Process for the production of isoindolenine derivatives



United States Patfit cfi PROCESS FOR THE PRODUCTION F ISOINDOLENINE DERIVATIVES Georg Riisch, Walther Wolf, and Heinrich Vollmann, 5

Leverkusen, Germany, assignors to Farbenfabriken Bayer Aktiengesellschaft, Leverkusen, Germany,' a manufacturing and trading organization of Germany No Drawing. Application September 4, 1952,

' Serial No. 307,906

This application is a continuation-in-part of our co- ,pendingapplication Serial No. 180,696, filed August 21 .1950, entitled l,-Amino-3,-Imino, Isoindolenines.

The present invention relates to new intermediate prodnets and to processes for their production, in particular it relates to new;phthalocyanine intermediates. t

It is an object of the invention to providenew intermediate products which may be used for the production of phthalocyanines.

A further object of the invention is to provide new intermediate products which may be used for the production of phthalocyanines under gentle conditions, especially at lower temperatures.

A further object of the invention is to provide very reactive new intermediate products which may be utilized in the organic synthesis.

A still further object of the invention is to provide new methods for the production of said new intermediate products.

Another object of the invention is to provide processes for the production of said intermediates on a technical scale.

Additional objects and features of this invention will become apparent as the following description proceeds. According to the prior art processes phthalocyanines have been produced by most various methods from most various starting materials. Important starting materials according to prior processes are, for instance, phthalic acid and phthalonitrile which are converted by the socalled urea-process or by the so-called dinitrile-process" into phthalocyanines.

It is supposed that the formation of phthalocyanines in the hitherto used processes passes various intermediates. However, extensive experiments carried out for determining the reaction mechanism have failed to prove-the presumed intermediates or to isolate them except monoimino-phthalimide fir;

ll 0 obtainable according to British specification No. 520,415, for instance, by heating phthalimide with urea and ammonium molybdate.

According to theoretical (Journal of the Society of Dyers and Colourists 61 (1945 page 71) thinks it possible that in the phthalocyanine synthesis an intermediate could be formed which contains 3 nitrogen atoms in one aromatic radical in a combined state and formulated this hypothetical intermediate as follows: a NH present invention besides phthalic acid and the functional considerations Haddock 2,739,155 Patented Mar; 20, 1956 Haddock expressly declares, however, that this intermediate or any other intermediates of the phthalocyanine synthesis except the aforementioned mono-imiuo-phthal- .im-ide could neither be isolated nor determined. 7

A. It has now been found that such hitherto unknown intermediate products of the phthalocyanine synthesis are obtained by heating o-arylene dicarboxylic acids, their nuclear substitution products or functional derivatives thereof in thepresence of substances giving oif ammonia under the reaction conditions, for instance urea, as well as in the presence of preferably at least equimolar amounts of anions which are stable under the reaction temperatures, whereby preferably nitrate ions amused and in case functional derivatives of o-arylene dicarboxylic :acids containing carbonyl groups or these acids are used asreactants, in the presence of catalysts promoting formation of phthalocyanine from o-arylene diearboxylic acids and, if desired, in the presence of inert solvents, to temperatures of about 200 C.

The intermediate products obtained according to the present invention are believed to be derivatives of isoindolenine. I t

N l H Their constitution is as follows: 21H IE2:

at N X .NH

. Q% C/ l l'Ha Ill'H IeSp:

i X N I C% Rz-N-Rg wherein X stands for hydrogen or for zero to four organic or inorganic radicals, for instance for alkyl radic'als such as CH3, CzI-Is, C4Hs, C5H11 etc., alkoxyradicals such as CH3O, C2H50- etc., aroxy, alkyl mercapto and aryl nierca'pto' radicals, heterocyclic radicals, further for halogen, -Nl-I acyl, -NO2, -COOH, --SO::H, '-SO2NH2, AOzNl-I alkyl, SO2N(alkyl)2 groups etc. X mayalso stand for one or two cyclic groups condensed to"'the benzene nucleus of the isoindolenine. One or more of-thecarb0n atoms of the carbocyclic nucleus or carbocyclic'nuclei may be replaced by hetero atoms, 'for instance by one or two N- orS-atoms. R1, R2 and R3 may stand for hydrogen or also for organic or inorganic radicals, for instance for alkyl radicals such as CH3, C2H5, C4H9, CaHn, C14H29 etc. These alkyl radicals may be substituted, for instance by hydroxy groups etc.,.for cycloalkyl-, aralkyland for aryl radicals such as phenyl, substituted phenyl radicals, naphthalene-or anthra'quinone radicals, for other polycyclic radicals, for heterocyclic radicals and for acyl radicals, such as formyl,

. acetyl, benzoyl etc. Furthermore, R2 or R3 may stand for --SO2 aryl groups. Rz-i-Rs may also stand for an alkyle'ne radical which may contain hetero atoms in its chain, for example the divalent radicals(CH2)sand -(CH2)2O(CH2)z- (both free valences being attached to the nitrogen atom). The radicals R1 and R2 (R3 respectively) may form a cycloalkylene ring, for instance R1+Rz may be (CH2)5-.

Aststarting materials for the process according to the derivatives thereof any of their nuclear substitution products containing the above mentioned radical X may be used. As polynuclear and heterocyclic o-dicarboxylic acids may be mentioned naphtha]ene-o-dicarboxylic acids, anthracene-o-dicarboxylic acids, pyridine-o-dicarboxylic acids, quinoline-o-dicarboxylic acids etc.

Of course, instead of the afore-mentioned dicarboxylic acids their functional derivatives may be used, such as, for instance, anhydrides, ammonium salts, imides, mnoimido-irnides, monoand diamides including ureides, o-cyanocarboxylic acids, whereby the carboxylic acid group may be present in form of said functional derivatives, and o-dinitriles. It is to be understood that the o-dicarboxylic acids, their nuclear substitution products or the functional derivatives thereof which are known as starting materials in the production of phthalocyanines according to the prior art processes may also be used as starting materials for the production of the amino-iminoisoindolenines according to the present invention.

When using dicarboxylic acids or their functional derivatives containing carbonyl groups as starting materials it is necessary to add a catalyst for carrying out the reaction. The same catalysts may find application which may be used in the production of metal phthalocyanines by the conventional methods, for instance, from phthalic anhydride, according to the so-called urea process. Especially suitable catalysts are molybdic acid or its salts, for instance, ammonium molybdate. On starting from o-arylene dinitrile the addition of a catalyst may be dispensed with.

The term substances giving off ammonia means the compounds which may be employed on carrying out the phthalocyanine synthesis according to the urea process. Such products are, for instance, urea, guanyl urea or biuret which are used in excess.

For accomplishing the reaction according to the present invention it is further necessary to add such anions to the reaction mixture as are stable under the reaction conditions applied. These are in the first line anions of inorganic acids, such as, for instance, of nitric acid, phosphoric acid, sulfuric acid, hydrochloric acid, however, good results can also be attained by means of anions of organic acids, such as, for instance, of aliphatic and aromatic sulfonic acids as well as of methane sulfonic acid, methionic acid, toluene sulfonic acid, and of naphthalenemonoand polysulfonic acids, for instance, naphthalene 1.5-disulfonic acid. These anions are to be used in at least equimolar quantities referred to the dicarboxylic acids or their functional derivatives. If minor quantities are employed the yield is generally reduced. Of course,

larger quantities than the equimolar ones may also be used without the yield being impaired thereby.

When using o-arylene dicarboxylic acids or their functional derivatives containing carbonyl groups as reactants it is of advantage to use nitrate ions which yield with the corresponding 1-amino-3-imino-isoindolenines insoluble, salt-like compounds which are less affected by changes of temperature. However, on using o-dinitriles as start ing material other anions yield equally good results. The said anions are advantageously charged in form of their ammonium salts or also as free acids which may be linked to the urea whereby it is of no consequence whether the anions are added to the reaction mixture already before or after the beginning of the reaction. In the production of the new intermediate products according to the present invention it is immaterial Whether the components are simply melted or whether a solvent is added. In the first case, the substance giving off ammonia which is preferably used in excess acts as diluent. In the second case, as solvents preferably higher boiling hydro starting material generally begins to melt. The reaction temperature may be raised to the temperature usually applied in the production of phthalocyanine according to the above described process whereby reaction is completed within a short period of time without phthalocyanines being formed thereby. Otherwise, the same conditions are applied which are customary in the production of phthalocyanines according to the above-said urea process.

Methods to be applied for isolation of the aminoimino-isoindolenines or their salts obtained according to this process differ somewhat depending upon whether the reaction has been performed with or without diluents. On working without diluents the melt is taken up with organic solvents, for instance, acetone, alcohols, water or in mixtures thereof, and is further diluted with water. The salts of the amino-irnino-isoindolenines already precipitate if anions yielding difficultly soluble salts, such as nitrateor aryl sulfonic acid anions were used for accomplishing the reaction. If, however, such anions were used as give easily soluble salts of the amino-imino-isoindolenines, the amino-imino-isoindolenines are preferably precipitated by addition of nitrate ions in form of their salts or by addition of concentrated'aqueous salt solutions, such as ammonium chloride-, sodium chloride-, or ammonium phosphate solutions.

When the reaction has been accomplished in the presence of solvents isolation may be effected by simply separating the amino-imino-isoindolenines from the solvents wherein the amino-imino-isoindolenines in form of their salts are insoluble. They may further be purified by means of solvents.

This process is described and claimed in our copending application Serial No. 180,696 of even date, entitled l,-Amino-3,-lmino, Isoindolenines.

B. The new intermediate products may also be obtained by adding ammonia or its derivatives to o-arylene dinitriles or the functional derivatives of o-arylene-dicarboxylic acids being free from carbonyl groups which may contain hetero atoms in the aromatic ring or to the nuclear substitution products thereof, if desired, in the presence of solvents and/or catalysts and/or under pressure.

Suitable starting materials for this reaction are besides phthalonitrile any of its nuclear substitution products containing the radical X-indicated in the above formulamay be used. As polycyclic and heterocyclic o-dinitriles may be named: naphthalene-o-dinitriles, o-dicyano pyridines, 2.3-dicyano pyrazine etc. Compounds containing four cyano group are also suitable such as 1.2.4.5-tetra cyano-benzene and 3.4.3'.4-tctra-cyano-diphenyl.

It is to be understood that all dinitriles or functional derivatives of o-dicarboxylic acids being free from carbonyl groups which are known as starting materials in the production of phthalocyanines may also be used for producing the new intermediates according to the present invention.

According to this process suitable derivatives of ammonia are for instance: primary and secondary amines such as methyl amine, dimethyl amine, ethyl amine, butyl amine, dodecyl amine, cyclohexyl amine, benzyl amine, aniline, amino diphenyl, naphthyl amines, amino anthraquinones etc., substituted amines such as alkanolamines, substituted anilines and substituted naphthyl amines. Furthermore, sulfonamides such as p-toluene sulfonamide, heterocyclic nitrogen compounds such as piperidine and morpholine, and N ,N -substituted hydrazines such as N- amino-piperidine, N ,N -diphenyl hydrazine may be used in the above mentioned reaction. Generally, the derivatives of ammonia are suited which are stable under the reaction conditions. The addition of ammonia or of said derivatives thereof to the aforementioned functional derivatives of o-arylene dicarboxylic acids being free from carbonyl groups, i. e. principally to the o-dinitriles, can be efiected in various manners. The temperatures applied am ss in'this reaction rarely exceed to 160 or 170 C. Thus, for instance, the said reactants may be' treated with ammonia or its derivatives without any additions and in the absence of solvents at temperatures above 100' C., preferably in the autoclave, under a pressure of up to about 120 to about 150 kg./cm. After completion of the reaction the excessof ammonia or derivatives thereof respectively is removed. The reaction product thus obtained is amino-imino-isoindolenine in technically pure form which may directly be used or previously further purified by treating with water or organic solvents. In order to facilitate purification it may be of advantage to carry out the reaction in the presence of inert organic solvents, for instance, of a low alcohol. Especially useful are alcohols containing at least one CH2OH group.

On using a higher boiling solvent, for instance, polyvalent amine, it is sufiicient to dissolve the starting material in I applied. The anions may be charged, for instance, in

form of their ammonium or urea salts, such as ammonium nitrate, ammonium chloride, ammonium phosphate and urea nitrate. In this case it is possible to carry out the reaction in the presence of urea or ammonia. When processing in this manner the corresponding salt of the 1- amino-3-imino-isoindolenine is produced which may be purified as described in the foregoing.

If a'catalyst is added, the reaction may also be accomplished at lower temperatures.

Suitable catalysts are heavy metal compounds, especially those which may be used for the production of phthalocyanines. As examples may be mentioned copper salts, especially salts of bivalent copper and salts of cobalt, nickel, iron, cadmium, zinc, or also activated metals, for instance, Raney-nickel. Also in this case, it is of advantage to carry out the reaction in the presence of a solvent and, especially, in the presence of monoor polyvalent alcohols, especially primary alcohols. The said catalysts are added to the solution of the starting material in quantities of about 01-50% calculated on the starting material used and the solution is saturated with ammonia or its gaseous derivatives mentioned above or a stream thereof is passed over the solution. When using liquid 'or solid derivatives of ammonia these may be introduced into the solution. In this case, the addition of special solvents may be dispensed with as,

"for instance, in the case of mono-ethanolamine. The reammonia or the said derivatives thereof to the said functional derivatives-of the o-arylene dicarboxylic acids being free from carbonyl groups. However, on using these products care has to be taken that the reaction temperatures are kept so low as to prevent the formation of phthalocyanine at all or, at least, to a material extent, i. e. temperatures up to about 100 C. are to be applied. Suitable metal alcoholates are those of alkali metals, alkalineearth metals and aluminiumwhereby the alcohoi compo same efiect is also attained by charging the said metal amides together with liquid ammonia or acid amides, such as formamide, acetamide. Mixtures of alkali metal or earth alkali metal alcoholates and formamide may also be used. The amount of alcoholates or amides respectively required for accomplishing the reaction may vary in a Wide range. Thus, for instance, it is possible to obtain good yields with 1 per cent or less of alcoholate calculated on the functional derivative of the o-arylene dicarboxylic acid being free from carbonyl groups. Similar yields are attained on using quantities corresponding to 1 mol of alcoholate per 1 mol of the afore-mentioned derivative or quantities exceedingsaid proportion.

Suitable solvents are in the'first line the lower monoor polyvalent alcohols, such as, for instance, methyl-, ethyl-, propyl-, butyl-, or amyl-alcohol or glycol or, as already mentioned above, acid amides or liquid ammonia. The said solvents may also be used together with indifferent solvents miscible therewith. Asexamples may be mentioned aromatic hydrocarbons such as benzene and toluene, furthermore tetrahydrofuran or diethyl glycol. On using the last-mentioned catalysts the optimum reaction temperatures vary in a wide range and depend on the character of the metal-alcoholate or -amide and of the solvents or solvent mixtures used. On processing with liquid ammonia the boiling temperature of ammonia is generally suflicient to accomplish the reaction whereas in other cases the optimum reaction temperature is at about 40 to 65 C. However, it may he sometimes of advantage to process at temperatures up to or above C. Care has to be taken that the upper limit of the reaction temperature is not exceeded since in this case the formation of phthalocyanine takes place. In spite of this fact, it is possible in some cases to operate within this critical temperature range if the reaction is performed within a .very short time so that only 1-amino-3-iminoisoindolenines are principally formed, i. e. if reaction is stopped before formation of phthalocyanine starts or directly after starting of the dyestuif formation.

amino-3-imino-isoindolenines are thus obtained.

This process is described and claimed in our copending application Serial No. 307,903 of even date, entitled Process for the Production of Isoindolenine Derivatives.

C. When using the last-mentioned catalysts the process may be carried out by reacting o-arylene dinitriles with the alcoholates in the absence of ammonia or amines to form the corresponding l-alkoxy derivatives of the 3- imino-isoindolenine which are described in the co-pending application Serial No. 180,695, now Patent No. 2,683,- 643, relating to Process of Dyeing and Printing and reacting the ,1-alkoxy-3-imino-isoindolenines thus obtained which may be monomeric as well as condensed ones depending on the reaction conditions applied, after isolation or also in the reaction mixture with ammonia or the aforesaid derivatives of ammonia (see part B). The monomeric or condensed alkoxy derivatives may carry nuclear substituents which are described in the above formula (see part A) under X. They may also contain hetero atomsin the carbocyclic ring and aromatic rings compounds in an inert organic solvent, such as, for instance, benzene, acetone or in alcohol, or the ammonia or the derivatives thereof are dissolved in alcohol and added to the solution of the alkoxy compounds. However, salts of ammonia or derivatives thereof may also be used which are reacted with the alkoxy compounds in form of their solutions. For accelerating the reaction it may be sometimes of advantage to process in the presence of some water in the reaction solution.

If monomeric alkoxy compounds are used for carrying out the reaction the monomeric amino-imino-isoindolenines are obtained. If, however, condensed alkoxy-irninoisoindolenines are employed as reactants, condensed amino-imino-isoindolenines may be obtained, if the reaction is accomplished within a short time. Condensed amino-imino-isoindolenines comprise compounds wherein one carbon atom each belonging to the heterocyclic nucleus of two molecules of the isoindolenine are connected by a nitrogen bridge and which may contain alcohol as an addition. They correspond to the formula wherein X is defined as in the above formula of part A, R being CH3, Cal-I5, CaHr, C4H9 or (Isl-I11 and other alkyl radicals and n being an integer from 1 to 6.

If the ammonia or the amines are reacted for a prolonged tirne and/or at higher temperatures, for instance up to about 160 C., the nitrogen bridge is split off and a further molecule of ammonia is added so that, for instance, in the case of the dimeric product two molecules of monomeric amino-imino-isoindolenine are formed.

When using primary amines as derivative for carrying out the above reaction, also the imino group of alkoxyimino-isoindolenine may be replaced by these primary amines.

isolation of the amino-irnino-isoindolenines thus obtained from the reaction solutions as far as they are crystallized may be accomplished in known manner by simply separating out. The non-crystallized portions may be isolated either after concentrating the solution, preferably in vacuo, or by adding the aforesaid anions forming difiiculty soluble salts.

Besides the said alkoxy-imino-isoindolenines also the corresponding thio-compounds may be used for carrying out the reaction with ammonia or its above mentioned derivatives. Thus, for instance, according to Porter, Robinson and Wyler (Journal of the Chemical Society, London, 1941, page 620) a mercapto compound is obtained which is indicated as o-cyano-thiobenzamide by addition of sodium sulfhydrate to phthalonitrile. The same compound may also be produced by reaction of anhydrous sodium sulfide upon phthalonitrile in methanol. The products prepared according to these two processes are believed to be l-mercapto-3-imino-isoindolenines. The corresponding amino-imino-isoindoenines are obtained by reacting the said mercapto compounds or the alkyl others thereof with ammonium nitrate in the presence of a solvent or suspending agent and isolating the nitrates of the amino-imino-isoindolenine thus formed.

Instead of using the said alkoxy-imino-isoindolenines it is also possible to charge alcohol-hydrochloric-addition-products obtained from aromatic o-dinitriles according to Pinner (Die lmidoather und ihre Derivate, Berlin 1892, page 2, etc.) which are almost identical with the above-mentioned alkoxy-imino-isoindolenines except that they contain hydrogen chloride in the molecule.

Hence it follows that in the reaction of the products obtained according to Pinner with ammonia or its derivatives which is preferably carried out in alcohol, care has to be taken that processing is done at very low temperatures, for instance, at 0 C. in order to avoid saponification by the hydrochloric acid present.

This process is described and claimed in our copending application Serial No. 307,904 of even date, entitled Process for the Production of Isoindolenine Derivatives.

D. In the production of the N-substituted derivatives of amino-imino-isoindolenines or its derivatives substituted in the carbocyclic ring as it is described in part A it is not absolutely necessary to start from dinitriles or the above-mentioned reactants, but these starting materials may also be reacted with ammonia to form aminoimino-isoindolenine which is not substituted at the nitrogen and the products thus obtained or their salts respectively may be reacted subsequently with the above mentioned derivatives of ammonia, for instance primary or secondary aliphatic, aromatic, cycloaliphatic, polycyclic and heterocyclic amines, which may be substituted such as alkanolamines, the derivatives of aniline or naphthylamines, etc., N .N -substituted hydrazines, furthermore piperidine, morpholine and hydroxylamine. This exchange reaction generally proceeds smoothly with splitting off ammonia. The reaction is most easily performed with primary amines whereby the reaction velocity is often satisfactory at room temperature. It is often of advantage to carry out the reaction in an inert organic solvent. Suitable solvents are in the first line alcohols, especially methanol or also water or formamide. When the reaction is accomplished by means of liquid amines, such as, for instance, ethanol amine, anisidine, an excess of these products may act as solvent. in the case of primary amines either the amino group alone or also the amino group and the imino group may be substituted. The weakly basic aromatic amines, for instance, aniline substitute the amino group only when the reaction is performed under gentle conditions. The imino group is substituted at higher temperatures and when the reaction is performed within a prolonged period of time. Mostly the reaction is accomplished at temperatures up to about 160 and 170 C.

On using strong basic, primary, aliphatic amines the exchange of the imino group is so easily effected that generally derivatives substituted at both nitrogen atoms can be isolated. On using secondary amines derivatives are obtained which are substituted at one nitrogen only. It is often possible to exchange the substituted amino or imino group vice versa by treatment with ammonia in excess against a non-substituted aminoor imino group. It is further possible to replace a substituted amino or imino group by amino groups substituted by a different radical. Also N-substitution products which contain different substituents on the amino and imino group may be obtained. By using aliphatic diamines such as polyniethylene diarnines products may be obtained in which both N-atoms of the amino and imino group are linked by a methylene bridge.

Isolation of the 1-amino-3-imino-isoindolenines thus obtained may be accomplished in usual manner, for instance, by simply separating the portions crystallizing out of the reaction solution. In other cases they may be precipitated and separated by adding solvents reducing their solubility and being miscible with the originally used solvent, for instance, hydrocarbons or ice water. However, anions may be added which yield difiicultly soluble salts, for instance, nitrate ions. Finally, the l-amino-3-iminoisoindolenines may also be obtained by distilling off the solvent used in the reaction.

This process is described and claimed in our copending application Serial No. 307,905 of even date, entitled Process for the Production of Isoindolenine Derivatives.

E. The new intermediate products are also obtainable by producing the yellow to red colored complex compounds containing copper frorn o-arylene dicarboxylic acids, which may also contain hetero atoms in the aromatic nucleus, or their nuclear substitution products capab le of f orrning phthalocyanine or their functional deabout 30' C with agents capable of dissolving monovalent copper directly or after converting same into the bivalent state. The treatment of the said complex compounds is preferably effected with nitric acid whereby advantageously during this treatment or subsequently anions are added which yield difiicultly soluble salts with the amino-imino-isoindolenines obtained according to the present invention.

Qo nplex compounds containing more than one atom of copperper one o-arylene radical obtained from o-arylene dinitriles and copper salts in the presence of substances giving off ammonia at elevated temperatures have already been known. Their production is accomplished in mo stvarious ways whereby compounds are obtained which depending upon the reaction conditions ap lied differ in their outer appearance, especially in color as well as intheir physical and chemical properties, for instance, solubility and reactivity. They may be more or less easily soluble or also insoluble in high boiling solvents,,,for instance, quinoline. However, all these corn- 'ponnds are characterized in that they contain more than one atom of copper per one o-arylene radical and that they yield the above-described new intermediate products of the phthalocyanine synthesis by treatment with agents dissolving monovalent copper directly or after converting sarne into the bivalent state.

The preparation of these copper complexes has been described, for instance, in FIAT Final Report 1313, vol. III, pages 342, 344, 345. According to this citationthey are obtained as difiicultly soluble to insoluble substances from phthalonitrile and cuprous chloride or cuprous bromide whereby more than one mol of the cuprous salt "be obtainedat room temperature or only slightly raised temperature. This process is carried out, for instance, by dissolving arylene dinitriles in a lower alcohol, for insta q ethanol and introducing gaseous ammonia after addingan excess of cuprous chloride (more than one mol of cuprous chloride per one mol of o-dinitrile). When using other solvents than alcohol which at least slightly dissolve the copper compounds in combination with the ammonia introduced, such as, for instance, ketones or tertiary amines, it is often necessary to process at higher temperatures. In this case it may also be necessary to apply the ammonia under pressure. Ammonia may also be replaced by its salts. As copper salts may be used, besides the salts of monovalent copper, the salts of. bivalent copper or the hydroxide of bivalent copper. The complex copper compounds obtained by means of bivalent copper compounds are mostly blue-gray colored.

Decomposition of the complex copper compounds is eifec'ted as already mentioned with agents capable of discalculated on one mol of phthalonitrile is used. The

mixture of phthalonitrile and the said cuprous salts is heated in the presence of urea and formamide at temper- .atures up to about. 180 C. They may be obtained quite generally from o-arylene dinitriles andcopper salts :in the presence of meat or formamide at about the same temperatures. The reaction may be carried out in the presence of solvents. For instance, nitrobenzene or chlorobenzene. However, on using high boiling solvents, for instance, quinoline, it is not necessary to add substances *giving off ammonia, for instance, urea or formamide but ammonia may be added in its gaseous form. Suitable reactants for the production of the insoluble copper-complex compounds are besides o-dinitriles, the corresponding o dicarboxylic acids, their nuclear-substitution products or also the functional derivatives thereof described heretofore. Incase the starting materials contain carbonyl zroups, the above described catalysts used in the production of .phthalocyanine according to the said urea process, for instance, ammonium molybdate and molybdie acidhave to be added. The optimum reaction temperatures may be varied between 140 and about 220 C. Instead of using the above-said cuprous chloride or cuprous bromide also other copper salts may find application, for instance, copper nitrate or copper acetate. In all cases the difiicultly' soluble to insoluble copper complexes "are obtained provided that more than 1 mol of the copper mentioned according'to which the complex compounds solving the complex-combined copper whereby the complexis destroyed. On the other hand, these agents shall not saponify the 1-amino-3-imino isoindolenines formed. For this purpose, mineral acids and alkali cyanides have proved to be most suitable. On using mineral acids processing is preferably carried out with anhydrous acids in order to avoid saponification of the new intermediate products, andat very low temperatures, 1'. e. preferably while cooling with ice, or the mineral acid is added in quantities only so that towards the end of the reaction the mixture shows no longer a mineral acid activity. Saponiiic'ation of l-amino-3-iminoeisoindolenines is especially prevented or reduced by the presence of anions yielding insoluble salts with the isoindo'lenines. Anions suitable for this'purpose are, for instance, those of nitric acid and of arylfsulfonic acids. Herefrom the particular advantages of the application of concentrated nitric acid for decomcentratedsulfuric acid containing some sulfur trioxide, or

Withmixtures of strong mineral acids with anhydrous organic acids. When the acid shows no oxidizing effect it has proved to be of advantage for achieving a smooth and fast reaction to add oxidizing agents, such as hydrogen superox-ide, or organic or inorganic per-acids. When using acids which" do not yield insoluble salts with the amino-imino-isoindolenines it is advisable for the above-said reasons to addthe anions forming difiicultly soluble salts, for instance, salts of toluene sulfonic acid, naphthalene sultonic acid or naphthalene disulfonic acid or also nttra'te ions already during decomposition. However, if decomposition is effected by means of alkali cyanidedit is not necessary to add the aforesaid anions since the 1 aniino-3-irnino-isoindolenines formed in the alkaline reacting alkali cyanide solution are present in form of free fats to] be capable of forming the corresponding complex alkalicopper cyanide compounds with the dissolved copper ions.

1 elation of the difficultly soluble salts of l-amino-3- iiriiiio-isoindolenines thus obtained may be accomplished by simply separating out. A preferred method of executionconsist's, for instance, in pouring after decompositioh of the copper complex compounds the mineral acid solutions onto ice or in diluting these solutions with water w'ith good stirring, the diflicultly soluble salts of l-amino- '3 irriino-isoindolenines immediately precipitating thereby. If'tl'ie above-said anions are not added during decompositioti 'i-ait'iino-fi-irnino-isoindolenines may be precipitated by subsequent addition of these anions, if necessary, after neutralization of the mineral acids from the aqueous solutions. Precipitation may be accomplished, for instance, by adding to the ice-water into which the concentrated acid is introduced, at least equivalent amounts of alkalies, such as ammonia, alkali lye, alkali carbonate or bicarbonate, for neutralizing the acid. If decomposition is effected with alkali cyanides the l-amino-3-imino-isoindolenines crystallizing may be easily separated in known manner after complete decomposition of the complexes.

The amino-imino-isoindolenines obtained accordingto the above described processes represent new products. They are generally colorless to yellow colored and mostly readily crystallize. They are stable and fast to storing in their crystalline form. Their melting points are generally above 100 C. On melting, in most cases, splitting off of ammonia or the derivatives thereof and decomposition take place, colored melts being left thereby.

The amino-imino-isoindolenines partly dissolve in water and in alcohols to form the corresponding hydrates or dihydro-alkoxy derivatives, i. e. they absorb one mol of water or alcohol. and in concentrated acid from which they may be recovered in form of their salts. These salts are more or less soluble in water, such as, for instance, the formates, acetates and chlorides; difiicultly soluble are, for instance, the nitrates, sulfites, phosphates, oxalates and the aryl sulfonic acid salts. The salts of amino-imino-isoindolenines wherein nitrogen is substituted often behave differently as to their solubility from the unsubstituted ones. The salts when heated are also soluble in a number of organic solvents, such as in substituted aromatic hydrocarbons, such as nitrobenzene, chlorobenzene and acid amides, furthermore in tertiary bases, for instance, pyridine. Also in this case, decomposition, i. e. splitting off of ammonia or derivatives thereof mostly takes place. The salts are generally difficultly soluble in aliphatic and aromatic hydrocarbons as well as in ketones, ethers etc. With dilute alkali lyes the hydrates or the free base respectively form alkali metal salts being easily soluble in water.

The l-amino-3-imino-isoindolenines are gradually saponified in aqueous solutions, the corresponding monoimino-arylene-dicarboxylic-acid-amides being formed thereby. Decomposition is promoted by heating or adding dilute acids or alkali lyes.

The salts of 1-amino-3-imino-isoindolenines generally contain one acid residue per one mol of isoindoleninehowever, salts have been isolated'containing less, for instance, /2 or Vs equivalent of the acid per 1 mol of iso indoleninewhich is mostly present in a combined state, for instance, in the case of nitrate. The salts may also be recrystallized from aqueous ammonia solutions under certain conditions. On the other hand, in any case, the free base or its hydrate respectively is obtained by adding equivalent amounts of alkali lye to the salts.

The 1-amino-3-imino-isoindolenines, as far as their amino group is not substituted, are accessible to many reactions of the primary amines. For instance, they may be acylated or alkylated. With diazonium compounds they yield diazo-amino compounds. They can easily be reacted with aldehydes. Aromatic o-dinitriles may be added in the presence of alkali metal alcoholates to form higher molecular products mostly containing alkoxy groups in the molecule. The 1-amino-3-imino-isoindolenines are converted with phenyl hydrazine into intensely colored compounds. On heating the 1-amino-3-iminoisoindolenines in high boiling solvents for a longer time ammonia or, if N-substituted compounds have been used, the derivatives thereof are split off and condensation products are obtained which contain i. e. tricyano cyaphenine. On heating the l-amino-3-imino-isoindolenines in pyridine-water-mixtures in the presence of sodium hydrosulfite generally blue colored solutions are obtained which by the action or excess sodium hydrosulfite or atmospheric oxygen easily decolorize again.

On heating solutions of amino-imino-isoindolenines Furthermore, they are soluble in dilute with reducing agents, for instance, with formaldehyde or if reducing agents are used as a solvent, for instance, formamide, more or less large quantities of metal-free phthalocyanines are obtained. On heating them together with metal salts and reducing agents the corresponding metal phthalocyanines are formed.

The monomeric as well as the condensed aromatic l-amino-3-imino-isoindolenines may be reacted with heavy metals forming complexes, if necessary, in the presence of solvents to form crystallizable complexes.

The 1-amino-3-imino-isoindolenines according to the present invention may be substituted as already mentioned above in the carbocyclic ring by one or more radicals. The compounds may also carry condensed aromatic or heterocyclic nuclei.

Besides the nuclear substituents the compounds may carry at the nitrogen of the imino and amino group the most various organic substituents.

The new l-amino-3-imino-isoindolenines-as far as they contain in the amino group an active hydrogen atom in a combined state-may be present in their tautomeric forms, i. e. a hydrogen atom is attached to the nitrogen bridge; in this case the l-amino-3-imino-isoindolenines show the constitution of the corresponding diimino-imides. In some cases, however, other tautomeric forms may also be present.

The invention is further illustrated by the following examples without being restricted thereto, the parts being by weight.

Example I 148 parts of phthalic anhydride are heated while stirring at ISO-160 C. for 20 hours with 300 parts of urea, 160 parts of ammonium nitrate and 0.3 part of ammonium molybdate.

The initially uniform melt becomes more and more granular. The reaction product which becomes crumbly towards the end of the reaction can easily be taken out of the reaction vessel before it grows completely cold. After cooling the hard reaction product is crushed, ground with water, sucked off and the residual amino-iminoisoindolenine nitrate formed in excellent purity is washed with water and dried. The yield amounts to 198 parts of amino-imino-isoindolenine corresponding to of theory.

Example 2 A mixture of 147 parts of phthalimide, 180 parts of urea, 90 parts of ammonium nitrate, 0.3 part of ammonium molybdate and 500 parts of nitrobenzene is stirred for 810 hours at 170 C.

After some hours almost colorless needles of aminoimino-isoindolcnine nitrate begin to precipitate from the clear yellow brown solution. About 10 hours later the conversion of phthalimide into amino-imino-isoindolenine nitrate is completed in almost quantitative yield. The reaction product is sucked off at 150 C., washed with hot nitrobenzene and methanol and dried. The melting point of the new intermediate product is at about 280 C.

For conversion into the free base C8H'1N3 40 parts of sodium hydroxide are introduced in portions with stirring at 0 C. into 208 parts of amino-imino-isoindolenine nitrate suspended in 1000 parts of water.

The granular mass is readily converted into a crystalline paste consisting of colorless needles of amino-iminoisoindolenine, which are sucked off and washed with some saturated common salt solution and dried.

140 parts of the free base are obtained. The aminoimino-isoindolenine melts at about 200 C. while splitting off ammonia.

Example 3 148 parts of phthalic anhydride, 160 parts of ammonium nitrate, 300 parts of urea, parts of nitrobenzenc and 1 part of ammonium molybdate are heated with stirring for one hour each at 150 and C;, then a 13 a t for another 115 hours at 160170 c. and at last to'r'z hours at 180-190" C.

Phthalic anhydride is dissolved during reaction, thereupon ,phthalimi'de crystallizes out and is completely .re-

dissolved. At last, the amino-lmino-isoindolenine-nitrate crystallizes almost quantitatively at reaction temperature. The thick paste thus obtained is stirred "with 200 parts of methanol at about 60 C., sucked fif, washed with methanol and dried.

A practically pure amino imino isoindolenine-nitraite is thus obtained in a yield of about 95 per cent o'f the theoretical.

Example 4 A mixture of '162 .parts of 'phthalic diami'de, 300 parts temperature, washed again with some acetone-watch,

mixture, "subsequently with water and dried. Aminoimino-isoindolenine-nitrate is obtained in excellent yield and purity.

Example 5 A mixture of 146 parts of mono-iminophthalimide, prepared according to British specification No. 520,415, Example 11, or according to Braun Berichte 40.2709, 120 parts of urea, 90 parts of ammonium nitrate, 0.3 part of ammonium molybdate and 500 benzene is stirred for about 6 hours 'at 170 'Aminjoimiho-isoindolenine-nitrate precipitated in "a good yield is sucked oil at about 150 C., Washed with hot nitrohen'zene and with cold methanol and dried.

1 Example 6 r A mixture of 147 parts of phthalimid'e, 180 par'ts of area, 206 parts of ip-to'luene sulfonic acid, 0.3 part of ammonium molybdate and 600 parts of trichlorobenzene is s'tir'red for 6-8 hours at 170 C. This mixture is diluted with hot chlorobenzene, the precipitated paste consisting of grey needles is sucked oil": while hot, washed with hot chlorobenzene and with cold methanol and water and *ubse- 'quently dried.

The salt of amino-imino-isoindolenine with'p-toluene sulfonic acid thus obtained is very diflicul'tl'y soluble in water and exhibits similar properties as the nitrate or the base, especially the capability of being easily converted into phthalocyanine.

, Example 7 I j 74 parts of phthalic anhydride, 150 parts of urea, 60 parts of methane ammonium sulfonate and 0.5 plut bf ammonium molybdate are heated for one'hour eah at 140, 150 and 160 C. and for another hours-at 170 C. After cooling the melt thus obtained is crushed, pasted up with methanol, sucked off, washed with some methanol and the methane sulfonic acid salt of aminoimino-isoindolenine thus obtained is dried. The'reacti'on product contains traces of phthalocyanine. The formation of phthalocyanine may be prevented by adding small quantities of an oxidizing agent, for instance, ammonium 'persulfate, to the reaction mixture after the initially 'pre- 'cipitating phthalimide has been redissolved.

monium perchlorate are added to the reaction mixture parts "or nitroalternated within the re sweater,

I matiiing 'r'ea"' ion time. The ffotmatidn of traces of "p'hthal oyanine is thus completely "brfalihost empathy-prevented.

The reaction m ture is radually eacted, 550 parts of tormamide are at! e art-20 C. and after stirrin oh'ce, 300 parent "methanol "are iitr'medi l'y added "to the mixture Whicha'fter thoiough stirring is rapidly cooled to room temperature, sucked 01f after 1--2 hour's. The reaction product obtained is washed with methanol and dried.

, The product represents ar'ni'no iiriino-isoindolenine-hy- The uritans off thebajsfe contained in the iil't'ra'te can {b precipitated as nitrate by stirring into ice cold, dilute m Exampleg "/0 parts "by weight of 223 tlimethoxy diphenyl. tdicarboxylic acid anhydride, z-sparts by Weight of ammutual hit'rate, 0:2 "part b t or ammonium tholybnae arerinneauceu i into a melt of '75 parts by weightdf rea'wh s g at 140 C. The terneeratu'reis swww raiseu ta i7o 0. After L2 hours a yellow precipitate fo rm's "the orah-ge colored solution. The stitfenin'g melt is diluted by addition of urea so as toremainrcapa'ble 'ofheiug stirred. After 6 hours 500 parts by volume of cold water are added to the men which -is 'cooled to l00" (2., the yellow precipitate of the resulting hit'ra'teof 1'-'-'amino-3=imino-5- (or *6*-)-(2.5'-

'dimethoxy r-tphenyl) =isoindolenine is suction filtered,

washed with cold water and dried. The Iyield amounts to parts by weight. .Thebase is prepared by mixing with stirring 70 parts ht of the uitrare and '140 parts by weight of P "4.8 partsby weight of sodium hi 1' parts by"{oIume or methan l, separating the so'di uin nit'ifz'ite "filtration and distilling off "the 'iii etha'nol in vaeuol The base remains behind as a yellow hias's in'a 'ciu ta'ti e yield.

x a Example J0 A mixture :0f-1'4=7patts.ofcphthalimide, 300 parts "of urea, 2-50 parts of sodium-n'aphthalene l-sulfohate and :1 part ofammonium molybdate are stirred into a solution of 50 parts of sulfuric acid in 500 partsof water. llhemixturew-is@hcatedto 150=-160 C. while distilling off the water and stirred at this temperature for about i Isolation isv achieved hystirring the cooled melt with about 2400 parts of methanol Besides sodium sulfate a part of the .ami-no-imino isoindolenine naphthalene-1- sul'fonate formed. does not ,go into solution. This part is sucked pfiand. the sodium sulfateis washed ofi? with water. The filtrate containing methanol is stirred into a mixture of ice, about 250 parts of the sodium salt of naphthaleneJ-sulfonic' acid a ntlSOO parts of glacial acetic acid. The reaction productdis'solve'd in methanol precipitates: thereby, as amino4mino isoindolenine naphthalenewl-sulfonate... Both parts are technically pure.

The products may further be purified by treating with benzene and with diluted solution of acetic acid and naphthalene-l-sulfonic acid.

v t 7 Example H 1 28 "parts of 'plithalonitiile are of ureaand parts of min in nitrate and stirred for 20 hour at -1-50='-160 "c. a cooled melt 'is made into a "paste with waterwlrerebyany acid, preferably melted with 240 parts nitric acid may be added iiii'til *thereaetion has-become neutral or weakly alkaline. Thenitrate of a'mipo i'minoisoindol'eni'ne formed whichts practically insoluble in 'cold water is sucked off'ahd washed 'with water. The product is obtained in excellent yield and purity.

I Exam le v 128 parts at phtuamnitrue, 300 parts of urea anti 132 Example 13 at 180 C. Towards the end of the reaction the melt becomes substantially crumbly and dry. The cold reaction mixture is stirred with water and weakly acidified thereby, sucked off after 10 minutes, washed and dried. 116 parts of technically pure amino-imino-isoindoleninenitrate are thus obtained.

The reaction product may be purified by recrystallization as follows: 50 parts of the technically pure product are suspended in 800 parts of water heated to 75 C., and 100 parts of 25% aqueous ammonia are immediately added. Aftervigorous stirring for 1-2 minutes the solution obtained is immediately run through a filter into a mixture of ice and 115 parts of concentrated nitric acid.

The precipitate formed is sucked off after 10-15 minutes, washed with some water and dried. 35 parts of analytically pure amino-imino-isoindolenine-nitrate are thus obtained.

Example 14 A mixture of 210 parts of the nitrate of pyridine-2.3- dicarboxylic acid, 188 parts of ammonium nitrate and 3.6 parts of ammonium molybdate is introduced at 140 C. within one hour into a melt of 300 parts of urea. The temperature is slowly raised to 170-180 C. and stirring is continued at this temperature for about six hours. After completion of the reaction the solution is cooled down to 100 C. and-cold water is stirred in. The crystallized nitrate of 4- or 7-aza-1-amino-3-imino isoindolenine is sucked off, washed with cold water and acetone and dried. The yield amounts to 190 parts of the nitrate.

For the conversion into the free base 100 parts of the nitrate are introduced at C. into 2000 parts of water and dissolved by adding 145 parts of a 17.9% sodium hydroxide solution, the temperature being kept at 0 C. by cooling. After a short time the free base precipitates in crystalline formand is sucked otf after 15 min utes, washed with some water, acetone and ether and dried in air or in vacuo. The yield amounts to 63 parts. The free base melts at 205-207 C. with decomposition.

Example 15 25 parts of 4-phenoxyphthalic acid are introduced at 110 C. into a melt of 12 parts of urea, 14.4 parts of ammonium nitrate and 0.3 part of ammonium molybdate and stirred for one hour at 175-180 C. until the initially formed long, thin prisms have been converted into short, coarse crystals whereby a mixture of 12 parts of urea and 12.4 parts of ammonium nitrate is still gradually added. The cooled melt is diluted with methanol and water, the precipitated nitrate of 5- or 6-phenoxy 1-arnino-B-imino-isoindolenine respectively is sucked off and washed with methanol and water. If any monoimino-phthalimide is present in the nitrate it-is removed by boiling off with acetone.

The free base is obtained from the nitrate by introducing same into a solution of sodium methylate in acetone, the base dissolving thereby. The base is precipitated from the solution by adding water.

The 5-(or 6-)phenoxy'1-amino-3-imino-isoindolenine melts at 99 C. and is very easily soluble in methanol and, contrary to most amino-imino-isoindolenines, also soluble in acetone. The product dissolves in dilute acetic acid with weakly yellow coloration. By adding ammonium nitrate and acetic acid the product is precipitated from its solution in acetone in form of its difficulty soluble nitrate in colorless, clustered needles.

Example 16 11.6 parts of 4.5-diphenyl-phthalic anhydride are introduced at C. into a melt of 5 parts of urea, 6 parts of ammonium nitrate and 0.1 part of ammonium molybdate and heated for one hour each at C. and 160 C. and for further 14-15 hours at 175-180 C. until the initially formed long, thin needles have been converted into small, coarse crystals. The melt somewhat cooled on standing is diluted with methanol, the nitrate of 5.6-diphenyl-l-amino-3-imino-isoindolenine is sucked oil and washed with methanol and acetone. The best method of isolating the free base consists in treating the nitrate with a solution of sodium methylate in dioxane.

Example 17 60 parts of urea, 55 parts of 3-chlorophthalic anhydride, 48 parts of ammonium nitrate and 0.5 part of ammonium molybdate are heated and worked up according to the method described in Example 14. 41 parts of the nitrate of 4- or 7-chloro-1amino-3-imino-isoindolenine respectively are thus obtained.

Example 18 A mixture of 56 parts of 4-phenylphthalimide, 60 parts of urea, 40 parts of ammonium nitrate and 0.3 part of ammonium molybdate is heated with stirring to C. until the melt has become crumbly. Heating is then continued at the same temperature without stirring. After heating for totally 20 hours the cold melt is stirred with methanol, sucked 011?, the reaction product is washed with methanol and dried. 65 parts of the technically pure nitrate of 1-amino-3-imino-5-phenylisoindolenine or of l-amino-3-imino-6-phenylisoindolenine are thus obtained.

Example 19 128 parts of phthalonitrile, 300 parts of urea and 125 parts of urea nitrate are stirred for several hours at about 150 C.

Further processing and isolation of the reaction product is performed as described in Example 11.

Example 20 204 parts of 3.4-dicyano diphenyl are added to a melt consisting of 480 parts of urea and 80 parts of ammonium nitrate and stirred for 30 hours at 150-160 C.

The cooled melt is ground with a solution of ammonium nitrate in water and acetic acid is added until the reaction has become neutral or weakly acid. The mixture is then sucked off and the product is washed with water. The phenyl-amino-imino-isoindolenine is ob- .tained in a very pure state and excellent yield.

Example 21 Example 22 .3'2 1 parts .of phthalonitrile .are heated with ,95 .6 .parts of liquid ammonia .in a stirring autoclave of chromenickel-.steel.for 5 hours at 11,0-l,18.C.,( abm1t;80.atmospheres overpressure). .After cooling the .NI-Is !is blown off and the solid, light blue-grey residue (37.6'Parts) is ground several times with water previously heated to 40-50 C. and sucked off until the residue has no longer a bitter taste. '-For removing any slight amounts of phthalonitrile theresidueisboiledoff with water, about 1.5 parts of deep-blue small needles :of practically metalfree phthalocyanine "remaining behind thereby. The aqueous extract .solidifies on-cooling to a viscous paste of colorless smallneedles .of aminorimino-isoindolenine which after sucking 01f, cautiously washing with some water2and.drying,.-melt at,-192195; C. 7

Example 25 128 parts of phthalonitrile-are heated to 140 C. with 80 .parts of anunonium.nitrate in 4000 parts of liquid ammonia while stirring'for'20 hours in an autoclave.

The crude amino-.imino-isoindoleninejnitrate. remaining after distilling vvolf the ammonia is purified :by treat- Example .125

128 parts of phthalonitrile are mixedzwith stirring with 250 parts of lycol and the mixture is saturated with ammonia at C. ,The dinitrile dissolves during about 24 hours whereas the glyc'olate of l-amino-B-iminozrisoindoleninea (CsHvNs-l -.GzHaOz) :icrystallizes; -.f1he gly- :colate: :isI-isolatd byrsuction zfiltration 2 atl 0 ..C.; Mashed benzene andzacetone. v When using-winiithe; above: reaction starting: materials ..:containing contaminations the mixture;aisheatedritolabout .C.-;towards ;tl1e;endi of :the reaction wherebytlthepreaction product dissolves rand tithe contaminationsican easily the; separated: off: ibynfiltr ation.

*The reaction :may: alsoibezconducted athishertempera- -.tures,. sawupzto. aboutf120 1C. -In;thiscaseitis preferuablezto dissolve theudinitrileuinrglycol andto addr;am- .cmoniaa at decreasing. temperatures.

;Ther:reaction;pro,ceeds in,1the.- same; manner .belo.w.1.50 C., however, therreaction'v times: are pro1onged.-in--.the.absence of catalysts such as alkali and metallic ions.

Example 26 1161 parts :of :phthalonitrilelare dissolved. in.5,0 patts-. of glycol; at. 130-140 ..C. and -.while'passing ammonia over the mixture. stirred for=2+3 hours-each: at.v 1207130" 0.,

wwithucooling. v I,

. The molecular, compound of. aminoriminorisoindolenine with gglycol ..CsH7N3.C2HsO2 vcrystallizes .in v. abundant uquantity in analytically. pure. form and; may;be;eas ily'..iso-

latedzby suckingoff and washing. with..acetone.

1-oxethylamino-3- .c ipitate as thick crystal paste.

Ex mple 7 13 parts of phthalonitrile and 01 part of copper chloride are stirred into parts of monoethanolamine. Phthalonitrile goes into solution and l-oxethylarnino-3- oxethylimino-isoindolenine crystallizes. The product can easily 1. i ola ed i q t e y eld y suckin and wasting -with. -al. 1-

Example 28 50 parts of phthalonitrile and 0,5 part of .coppersulfate are suspended ,in '250 part s of methanol and the .-mixture.is saturated with ammonia. Phthalonitrile grad- ,ually dissolves ,at 20-70" C. A blue-grey, finely :crystalline copper ,complex salt of ,aminodmino-isoindoleriine pr cipitates- .M e e :3 pa of t ee iha =CsH7N; precipitatein coarse crystals. Thechiet portion remaining .dissolved .can be precipitated :as nitrate by t qg-t erm x u e i t .w y-a d fi d wate eqata nitrate. -zquantita ivetal yi l is ob a ned- The reaction proceeds more slowlyin formamide hgw- ..ever, g a ly be p f rmed in ot e alcgh9l's su h l a 1 S mil o e te re u tiareatta on p eCu Q bro cvpp rsa t ,s ch'a $2149 CuClz, 2H2O, CuNO3.3H2O, 'glycocoll copper, acetylacetone-copper, or also ,salts .of copper, nickel, cobalt, admium -.e o a ti me ls o in an e Ra y- -.nic.kelnependins .o th conditions applied .t

.-a t ond accon plish d w t n .2' 1.

Example .29

jAsodium methylate solution consisting of'3 parts of sodium and '128 .parts of anhydrous methanol is pou red onto 128 p arts of phthalonitrile.

is poured onto 128 parts phthalonitrile.

The mixture is vigorously stirred with cooling-however, towards the end of .the reaction which is accom- 3 parts of sodium and;12 8 parts of anhydrous methanol plished within a few minutes the temperature is allowed -to -raise -up to *50" 'C. or also up to-theboilingpoint of 1 the mixture. The color of the mixture --changes thereby from yellow t o-orange and finally-to deep dark red brown. "As soon as the phthalonitrile has completely a dissolved the temperature is reduced below -50 C. and gaseous ammonia is passed ;over thesolution with stirring. After some time 1-am ino-3{minodsoindolenine begins to pre- The mixture is further stirred forsorne hours, diluted with 1 28-;parts'of--acetone,

"further; saturated with ammonia, the temperature is low- 'erecl-to"0 C.,the-solution is sucked OtLthe precipitate is wa'shed-with acetone until the washing has become colorless, and dried.

100 to parts of -1:amino-B-imino-isoindolenine corresponding to 70% of the theoretical ars thus obtained.

The product ityellowish colored. A. completely color- "less; product is'obtained by carrying out the reaction at lower temperatures-with one and-ahalfto two times the quantity of alcohol and three to five times thetquantity of sodium, the yield being somewhat impaired thereby.

The portions of-the reaction productremaining dissolved after sucking ofland washingrnay be precipitated -asnitrate.

vExample 30 '5'0 parts ofsodium .are dissolved in-320 parts ofeanhydrous ethyl alcohol. The mixture .which :solidifies after'cooling is dissolved in 1130parts .of formamide. ,zAt =-50-"C. 204 parts of 3.4-dicyano diphenyl are introduced -:-with;- stirring until after a fewhours the adinitrilehas dissolved. Thereaction mixture soon solidifiesto a cryst'al-paste'which is cooled and kept at room temperature for several hours. The precipitated product is -,:separated --.by suction, the part remaining dissolved is precipitated by addipg water. The monqhydrate of 1- amino-3;iinino- S(or;el-phenyl-isoindolenine isobtained in excellent purity and yield from both parts by recrystallization from a mixture of acetone and Water (about 1:1).

Example 31 parts of calcium are dissolved in 400 parts of anhydrous methanol. 1130 parts of foramide are added at room temperature, whereupon 128 parts of phthalonitrile are introduced.

The solution is stirred for a few hours at 70-80 C. The initially yellow solution which changes to yellow green is introduced when cold into a mixture of ice, ammonium nitrate and nitric acid. The precipitate formed thereby is sucked off and washed with water. After drying the crude produce is boiled out with acetone and sucked off again. The nitrate of the amino-iminoisoindolenine thus obtained is not yet quite pure. Purification may be achieved as indicated in Example 13.

Reaction may also take place without the use of alcohol in such a manner that the calcium is dissolved in formamide at temperatures of about 70 C. the phthalonitrile is introduced with stirring after cooling.

When working in this manner the possibility of dyestutf formation being initiated is much greater.

Example 32 14 parts of lithium are dissolved in 400 parts of anhydrous ethanol. 1130 parts of formamide are added at room temperature and 128 parts of phthalonitrile are introduced with stirring.

The reaction mixture is heated for some hours at 70-80 C. Further processing is done as indicated in Example 31. The nitrate of amino-imino-isoindolenine is obtained in a yield of 80% to theory. Similar conditions as indicated in Example 31 with regard to calcium may be applied in a reaction carried out without alcohol.

Example 33 46 parts of sodium are dissolved in 800 parts of anhydrous methanol and after cooling there are introduced with stirring 128 parts of phthalonitrile dissolving with slight self-heating. Into the mixture is stirred a solution of 342 parts of p-toluene sulfonamide in 800 parts of anhydrous methanol and the mixture is heated for 4 hours at about 90 C. The 1-p-toluene sulfonamino- 3-imino-isoindolenine is thus formed.

By stirring the reaction mixture into an ammonium salt solution cooled with ice the reaction product precipitates. The precipitate is purified by boiling out with ethanol and with benzene. This sulfonamide compound does not form a difiicultly soluble nitrate.

Example 34 128 parts of phthalonitrile are introduced into a mixture of 86-90 parts of piperidine and a sodium methylate solution consisting of 2 parts of sodium and -50 parts of methanol.

The phthalonitrile dissolves Within a very short time. The heat being set free is discharged to such an extent that the temperature raises only to about C.

The l-piperidino-3-imino-isoindolenine precipitates in colorless needles already at the reaction temperature or after cooling. Isolation is effected by diluting the reaction mixture with 80-10() parts of acetone. The mixture is sucked off when cold and the precipitate is washed with cold acetone and benzene. The product obtained is analytically pure and shows a flash point of 120 C.

On replacing piperidine by morpholine the reaction yields 1-morpholino-3-imino-isoindolenine. The product decomposes at about 140 C. with blue coloration. It forms with ammonium nitrate 1-amino-3-imino-isoindolenine nitrate.

Example 35 46 parts of sodium are dissolved in 800 parts of anhydrous ethanol. 430 parts of piperidine are added and and 20 204 parts of 3.4-dicyano diphenyl are dissolved in the mixture with stirring and heating.

The solution from which impurities, if any, may be removed by filtration is heated for 2-3 hours at about 90 C. and then cooled. The reaction mixture from which on longer standing small amounts of the base formed precipitate is then stirred into a mixture of ice and 200 parts of nitric acid. The nitrate of the S-(or 6-) phenyl- 1-piperidino-3-imino-isoindolenine is thus obtained in good yield. The precipitate is sucked olf, washed with water and dried. The product may be recrystallized from an alcohol-benzene-mixture (about 1:1). The nitrate melts at about 2l5-220 C. with dark coloration.

According to elementary analysis the compound exhibits the following composition:

calculated for found reHzoOsN4 C=64. 05% C=64. 74% H= 4. 20% H== 5. 72% N=15. 85% N=15. 91% O=14. 28% O=13. 63%

By replacing piperidine by morpholine, aniline, dimethylamine well crystallized compounds are obtained in good yields.

Example 36 0 cipitate at this temperature. The product is most easily isolated as nitrate by stirring the reaction mixture into cold dilute nitric acid. The following values for the nitrate were obtained according to elementary analysis:

calculated for CrzHrsOsN;

o=55. 22% 0 =54. 51% H= 6.44% H= s. 11% 0=1s. 20% O=l8. 17% N=21. 20% N=21. 21%

Example 37 parts of pulverized sodium amide are introduced into 850 parts of formamide in portions at 0 C. while stirring and cooling with a freezing mixture of ice and sodium chloride. 128 parts of phthalonitrile are added in portions to the clear solution and the temperature is raised to 6070 C. A yellow solution is obtained from which colorless prismatic needles precipitate.

After 6-8 hours the solution is cooled, the amino-iminoisoindolenine obtained in good yield is sucked off, washed with some formamide and acetone and dried. By introducing the filtrate into a mixture of ice and nitric acid containing as much nitric acid as is required for neutralization and salt formation, a further quantity of aminoiminoisoindolenine is obtained as nitrate.

Example 38 80 parts of pulverized sodium amide are introduced in portions at 0 C. into 1130 parts of formamide while stirring and cooling with a freezing mixture of ice and sodium chloride. 204 parts of 3.4-dicyano diphenyl are gradually added to the solution. The temperature is then slowly raised to 50 C. A yellow solution is formed from which grey crystals precipitate. After about 6 hours the solution is cooled, the hydrate of phenyl-amino-iminoisoindolenine obtained in almost quantitative yield is sucked off, washed with some, formamide and acetone and dried.

- arsa 1255 .Examplef39 Y 311222 'parts of sodium i amide \are introduced "into ="'If50 f partsof formamide at Cwwith'cooling and'stiri ing. 30 t parts of- 4iS-dichlorophthalonitiile are added in portions to-the clearsolution. After gradually raising the temperature to 40 C. and stirring at this temperature for 12 hours "the mixture is cooled and sucked ofif, the precipitate obtaine'd is washed with acetone and ether and dried. The yield amounts to 27 parts of4,5-di'chloro'- l-amino 3-iminoisoindolenine decomposing at "about '265" C."-wlii1e'splitting off ammonia.

Example 40 60. .parts of forrnamide, :3.5 parts. of sodium ,amide. and 107 parts of'3.4-dicyanodiphenylsulfone are reactedias described. in Example 39. 9;.parts of 1-amino-.3;-iminoiso- .indoleninyl-S or -6-.phenylsulfone decomposing at--a bout .2l" C.while splitting oifarnmonia are thus obtained.

Example 41 .32 parts of pulverized-sodium amide are. introduced in .portions. into .320 parts of.-formamide atIO" 'C. withstirring and cooling with a freezing. mixture of ice. and-common salt. 53 parts of -A-4.5-4-methyl-tetrahydrophthalonitrile. are-added in portions to the clear solution. The temperature is allowed to raise to room temperature, where- .by colorless crystalsmoreand more precipitate fromthe initially yellow and then violet red colored. solution. .After about 12 hours tetrahydrated amino-imino-methylisoindolenine formed is sucked o fll'and washed with acetone and.

-.ether. The product decomposes at about 130C. while -splitting ofl ammonia.

:The new substance is converted-into the corresponding .tetramethyloctahydrometal-phthalocyanine by: means of .metal salts, for instance, saltsof copper,. nickel. and .co-

halt, in the'presence of glycol or formamide,-.already at .temperatures of about 100 C. The new phthalocyanine .dissolveswin.concentrated sulfuric acid with.:blue .colorration. 0n gently heating theblue solutionchangesto :brown, tetramethyl-copper-phthalocyanine being formed .with further dehydrogenation.

If, however, the tetrahydrogenated .aminoriminomethyl- ..isoindolenine is heated in nitrobenzene in thegpresenceof a copper salt for alonger time 'tetramethybcopper- ,phthalocyanine is immediately obtained.

. Example 42 15.6 parts of sodium. amide are dissolvedatf0 .C. with cooling and stirring in '90 parts of formamid. I7L8 parts of 1.2.4.5-tetracyanobenzene (prepared from pyrromellitic acid tetraamide byconventionahmethods) .are added in smallgportions to .the clear solution. .A. deep red solution .is formed from which 'yellow, prismatic needles". soon prercipitate which are sucked oif after one. hoursstirring. at

. room temperature, washed with some formamideand ace- -.tone. and dried. 'The benzodi(amino-iminopyrrolenine) :obtaincd in1g00d yield decomposes .onheating without :xmelting.

Example 43 40'parts of sodium amide are dissolved at 0 C. in

22 .cride isgaassedsover .the: mixture at:5--10 C..for -48. hours .andmthe.crystallineprecipitate is sucked 01f, washed with .zdry-lbenzene and dried invacuo. :The yield amounts to 40 parts of the imino-ether thus obtained are introducedratO C. into-a solution of 50 parts of ammonia in 4001 .partszof methanol and the methanolis .evaporated cinvacuo.

.44. .partsof a residue which is dissolved at 0 C. in 200 .partsof about 80% nitric acid are obtained. On pouring the solution onto. small piecesof ice'the nitrate of 1- ..aminofi-irnino-isoindolenine is precipitated, sucked .ofi, .washedwithwaterand dried in .air. 7

-Replacing phthalonitrileby the equivalent quantity of 3.4-dicyanodiphenyl the nitrate of l-amino-B-imino-S-(or -6-) phenylisoindolenine is obtained.

Example 45 1.02.4..parts of, .phthalonitrileare introduced at C.

:20 .intoasolution of 4.6; partsof sodium .in8l .partsof meth- .:anol..diluted with 450 partsofvbenzene. .Stirring is .con-

-.. tinued until the :phthalonitrile. has been dissolvedawith yellow coloration. .Thereupon 20.4 parts-of ammonia (.100%) .dissolvedinmethanol and 0.9 part of =wate1' ..are..added. and it is further stirred at 20 C. until. a test .porttiongives no longer a stable, blue lcuco compound in .methyl .alcoholicaqueous. solutionwith dilute sodium hy- :droxidesolutionr and sodium, hydrosulfite. .64.4 parts of .tormic-acid are allowedto run into the solution which is formed. is sucked ofi,-washed with-benzene and dried in vacuo. About. 167.7 partsxof formate correspondingto 94.5,.parts of Lamina-3-iminorisoindolenine or 85.6% :of the theoretical are. thus obtained.

Byreplacing formic. acid by equivalent amountsof .other carboxylicacids corresponding .salts of the acids are obtained.

Example 46 35.6 parts of IZZ-dicyanonaplithalene are-- introduced into a solution of 1.15 parts of -sodium"in .4 parts of methyl alcohol diluted with 18225 parts of benzene and '-'stirred-until the I IZ dicyanOnaphthaIene has been dissolved with yellow coloration. Thereupon '20.4 partsof'am- 5 "monia-(l 00%) :=dissolvedin methanol are added and '300' parts of formamide with stirring. parts of 3.3'.4.4'-tetracyanodipl'ienyl are added in portions tothe clear solution and gradually heated to 4060 C.'. a yellow-brown solution being formed thereby. Afterabout one hours stirring the solution is cooled with ice. Di- (amino-imino-isoindoleniney]) precipitates in nearly quantita'tive yield in yellow, fine, small needles, which are sucked off, washed'with some t'ormamide andacetone anddried. Di(amino-imino-isoindoleninyl) decomposes 'on' heating without melting.

Example 44 64 parts .of phthalonitrile are dissolvedat 10 .in .--r2000,.parts. of anhydrous benzene: and-23 parts :of r abso lute: alcoholareadded. .Thereupon dryfhydrogen chlostirre'duntil attest portion givesno blue leuco compound in methyl alcoholic, 'aqueous solution. "The precipitate obtained in a good yield '(amountingto 70% of -the theoretical) is su'ckedoff andwashed'with benzene and 50 ligroin and driedin vacuo. The crude productis'obtained 65 difii'cultly soluble nitrate in yellow needles by addingam- -monium'nitrate. It is'soluble in dilute-hydrochloric acid -with yellowcoloration'but precipitates again immediately as yellow hydrochloride which "is' converted into colorless needles on boiling.

Example 47 11 .0 parts of -3 .4'-dicyano-(C)-phenyl-6-methyl benz- 1=thiazol :are introduced into asolution of"0.23 partxof :gsodiumdn 55.4:parts ofimethanol diluted with 45'.6 parts .-:of1:benzene and 1; stirred '.until -..'.the starting zproduct alias almost completely been:.dissolved. .Thereupon 4'.1'2.;parts of ammonia (100%) dissolved in methanol are added and the solution is kept at 35-40 C. until a test portion gives no longer a blue leuco compound. The crystalline precipitate is sucked d, washed with benzene and ligroin and dried in vacuo.

Amino-imino-isoindoieninyl-methylbenzthiazol is obtained in a yield of about 90% of the theoretical as greenish grey powder containing already small quantities of phthalocyanine and slightly dissolving in methanol and acetone. The product is soluble in dilute acetic acid with weakly yellow coloration and precipitz-ttes as slightly soluble, weakly yellow nitrate when adding ammonium nitrate solution. The melting point of the product containing about V2 molecule of methanol is at about 262- 264 C.

Example 48 18.96 parts of 4-methoxyphthalonitrile are introduced at 20 C. into a solution of 0.69 part of sodium in 12.1 parts of methanol diluted in 67.5 parts of benzene and stirred until the starting product has been dissolved with yellow coloration. Thereupon 12.24 parts of ammonia (100%) dissolved in methanol are added and stirring is continued until a test portion gives no stable blue leuco compound in dilute sodium hydroxide solution and sodium hydrosulfite. The solution is then concentrated to a small volume in vacuo, the crystals precipitating after some time are sucked off, washed with benzene and ligroin and dried in vacuo. 5-(or 6-)methoxy-1-amino-3-iminoisoindolenine is obtained in good yield in rod-shaped colorless crystals becoming green at 180 C. and decomposing at 202 C. The S-(or 6-)methoxy-1-amino-3-imino-isoindolenine is soluble in Water, soluble in methanol, ditficultly soluble in acetone and gives a slightly soluble nitrate. The portions of the product remaining in the benzene mother liquor may be precipitated by adding ammonium bicarbonate.

The melting point of the carbonate extracted from the crude salt mixture with methanol and precipitated with v acetone is 258-261 C.

Example 49 2.3 parts of sodium are dissolved in ethanol and the solution is concentrated to 18-23 parts, stirred with 52-64 parts of liquid ammonia at about -30 C. and 12.8 parts of finely ground phthalonitrile are rapidly stirred in. The starting product is almost completely dissolved while extracting ammonia by vigorously boiling and 1-ethoxy-3- imino-isoindolenine is then precipitated. The reaction product is isolated after 10 minutes by diluting the reaction mixture with 100 parts of ice-l-water, sucking off, washing with water and drying in vacuo at 30-40 C., in a yield of 92% of the theoretical. 16 parts of diethoxyimino-dihydro-isoindolcnine thus obtained are heated with 36.4 parts of concentrated aqueous ammonia on the waterbath. The product is dissolved within 3 minutes at 60- 65 C. Traces of non-dissolved portions are removed by filtering and the solution is chilled. A thick paste of colorless, almost rectangular small crystals, which are visible by means of a microscope, is formed. The product slightly soluble nitrate precipitate.

On replacing ammonia by methylamine, dimethylamine, other monoand dialkylamines or piperidine and morpholine the reaction yields a series of well-defined products wherein not only the alkoxy, but also the imino-group is partly exchanged against alkylamino or alkylimino radicals.

In the above reaction phthalonitrile may be replaced by 3.4-dicyano-diphenyl or 4-methoxyphthalonitrile. In this case the reaction yields the corresponding nuclear substituted l-amino-3-imino-isoindolenine derivatives.

Example 11 parts of diethoxy-imino-dihydro-isoindolenine are heated with '56 parts of aniline on the water bath as described in Example 49. The starting product dissolves within 10 minutes at about C. with a deep yellow coloration and presently light yellow small crystals precipitate. After stirring at C. for another 15 minutes the solution is cooled down to 20 C., sucked off washed with methanol and dried. About 7 parts of 1-anilino-3- imino-isoindolenine forming greenish yellow, coarse small crystals melting at about l90-207 C. with decomposition and orange coloration are obtained.

On acidifying the filtrate obtained as described above with dilute hydrochloric acid a slightly soluble, full, yellow colored hydrochloride precipitates. According to analysis the product obtained is a monohydrochloride of l-phenylarhino-3-phenylimino-isoindolenine.

Example 5.1

7.1 parts of 4-methylphthalonitrile are introduced at 20 C. with stirring into a solution of 0.29 part of sodium in 5.05 parts of methanol diluted with 28.1 parts of henzene and stirring is continued at 20 C. until the intensity of the yellow solution is not further increased. Thereupc-n 1.28 parts of ammonia dissolved in methanol are added and stirring is continued until a test portion gives no longer a blue leuco compound with dilute sodium hydroxide solution and sodium hydrosulfite. The crystallized 5-(or 6-)methyl-1-amino-3-imino-isoindolenine is sucked off and washed with benzene and ligroin. The product yields colorless, full, long prisms becoming green blue at C., sintering at 18l-l82 C. and decomposing at 189-190 C. with blue coloration.

The portions of the base remaining dissolved in the original reaction liquid may be precipitated with formic acid as formate which may be purified by dissolving in water and precipitating with acetone.

Example 52 80.7 parts of a methanol solution containing about 8.0 parts of anhydrous sodium sulfide are mixed with 12.8 parts of finely distributed phthalonitrile at 20 C. The temperature rises within 15 minutes to 35-40 C. While the dinitrile dissolves with deep yellow-temporarily deep green-yellow-c0loration. The solution is stirred for another quarter of an hour and 20.0 parts of glacial acetic acid are gradually added drop by drop, the addition product formed thereby precipitating in crystalline form with brownish coloration. The product is sucked off and washed with methanol. The yield amounts to 13.4 parts of a product which takes on heating a very dark color and sisters at 220-225 C. with decomposition. One part of a somewhat less pure product still precipitates from the mother solution by adding water. According to its chemical behavior, mode of origin and elementary analysis the product formed is the mercapto-imino-isoindolenine or in the tautomeric form imino-thio-phthalimide. With aqueous sodium hydroxide solution an orange colored sodium salt is obtained being ditlicultly soluble when cold and dissolving on heating with orange coloration. The product dissolves in pyridine with red coloration and can be crystallized from this solvent. The pyridine salt first precipitating thereby decomposes on Washing with methanol and shows again a light gray brown is. obtained which. temporarily dissolvestonheating,.:how-

ever, after some time deposits. in .redd-isl greymeedles,;.presumably consisting of vthiophthalin'lide and phthalimide.

With methanolic sodiumhydrosulfide solutionprepare'd by cold saturation of -a solution of *anhy'drous NatS in methanol 2 with H28 and filtering on the precipb :tate'd= sulfur-the mercapto imino-isoindolenine "described therein is obtained onheating'within'ashort time. In'this v case the product 'idepo'sits directl-y on cooling as orange --'colored sodium salt.

="On boiling the mercapto imi-no-isoindolenine in nitrobenzene for ashort time blue needles with a'metallic lustre of metal-free phthalocyanine precipitate, hydrogen'sulficleesoapingthereby.

' 16'f2 parts of mercapto-imino isoindolenine in 147 parts of; pyridine are mixed with l-2-parts of ammonium nitrate '-'With stirring. Bygentlyheating'on the Water-baththe starting product dissolves within 10 minutes; an almost colorless compound -pre'c ipitating from the red brown "solution in a crystallineform. "After stirring forhalf an '='hour at 90"Csthe solution" is sucked olf, the-precipitate is washed ""with pyrid-ine until "clear, 'washed "again with water-anddried. The almost colorless residuecrystallizes from dilute aqueous ammonia-in colorless' 'needles "and displays all properties :ofvthe amino-imino-isoindoleninenitrate.

Example 5 3 11.000 parts-of acetamidean'd 1281 parts of phthalonitiile ware introduced into a solution ct -"1 50 parts ;.of potassium ihydroxide in '400 parts of technical" methanol. "The-soluztion thus obtained-is heated for sometime at'70 C. I and uis stirred -still -hot into a mixture o'f l000parts of am- :monium: nitrate: and ice. The precipitating amino iminoisoindolenine nitrate is sucked off, washed with water rand drie'd. By boiling out with "benzene and acetone the reaction product is obtainedin' good purity.

'Exam ile'54 145 parts of amino-imino-isoindolenine are stirred with '"500 parts of aniline 'at350*60 C., the base slowly dis- :solving and anilino-iminoisoindolenine*or its tautometic forms crystallizing thereby "while -gaseous ammonia escapes.

After hours the solution is cooled with" ice, su'cked off, the precipitate ZiS washed with 'methanol or acetone and dried. The light'yell'ow 'product melting at 208" C. is obtained in analytically pure form. The -yield amountstd95 ofithetheoretical.

ncarrying 'out the reaction 1 in bo'ilinjg 'me'thanol the :quantity' of *aniline may" be reduced 'to about "100 parts.

145 parts of amino-imino-isoindolenine and 5200::parts of anilinesare heated:with:stirring.

he'rmonosubstitution product 'temporai'ilyrcrystallizing :and :rredissolving 1011 further lheating *is initially ifOI'Il'lBd :With rsplitting.olfaoframmonia. The temperatureiis rth'en *rr'aised to 200 C. and *the solution is kept :at Jthis temdeep yellow .colored. ..The product .is obtained in a a guantita'tive yield.

Ilhe laddition product .of .1 -mol of. aniline ...to .1 ,moltof phenylamino .3- phenylimino -.isoindolenine. temporarily -:ctystallizessundertheasaidmonditions. .This productzmelts Q26 .-..at.7.i8 7-9 1C. and splits off againwtheuadded aniline at :Example 56 "20 "parts "of an'iino irnino-isoindolenine -and "30 parts ofo-anisidine are heated with stirring as"fast as po'ssible in VieW'ofthe'actiVe splitting on of ammonia a'n d the "solution'is'kept at -150 C.'for minutes, 'the=:base --charged being initially dissolved in anisidine. Presently "theueactiomprdduct crystallizes already at thereac'tion temperature. The reaction mixture is then'cooled,-'stirred with methanol,-sucked o'if whenice-cold,the precipitate is-'-wa'shed"with methanol and" dried. 'O Methoxy-anilinoimino isoindolenine or its' tautomers respectively are ob- "tained in analyticallypure form. "The'lightyellowprod- 'uct'me'lts at 195-200 C. 1

:Example 57 parts of amino imino-isoindolenine and pa'rts;of 'm-anisidine arheated with stirring at 150 'Cu-until after "30 to minutes'splitting oiiof t ammonia ispra'ctically complete.

The 'coldy'deep yellow melt is'diIuted with methanol and the deep yellow chloride of m-methoxyanilino-m- 'methoxy phenylimino isoindolenine is precipitated by means of 'hydrochloi'icacid.

-'Example 5 8 5 *parts ofamino imino-isoindolenine are gently heated with excess cyclohexoxypropylamine (cecsHuOcaHeNl-lz) '=with stirring. At -80 .C. ammonia readily escapes.

.'added, the starting product being immediately dissolved thereby. "Impuritiesin'the solution are sucked off'as fast as possible and the filtrateris5stirred for some time. Ox- ...ethylamino oxethylimino -isoindolenine obtained .in a .guantitative yieldis vcolorlessan'd melts at 196 C.

.:In Iformtoftthe free ,basetthe product.is insolublein most customary solvents when cold.

Theireaction may also be accomplished ..in aqueous soln'tion.

-Example60 I .320iP3I'1S10f iaminoeiminodsoindolenine are reacted with 40 quarts ".of apenitran'iline win boiling glacial acetic acid. .ilkfterxthesstarting :productwhas 1 initially been 1 dissolved 1.4 -.niti:ophenylamino--:'3J4" nitrophenyl --imino isoiindolenine. precipitates: in light yellow, small needles melt- Eingsatlil 1-..3 1'2 -1C.

The product yields a..so'dium .saltcrystallizing :from :aqueouszmethanolrin long, :deep :red needles which is :hydrolizediagain with much water.

Example 61 40.0,.parts of copper .acetate .are dissolved .with. stirring at ..l20 LC..in 45.00parts .of .formamide; 1128 parts .of phthalonitrileiare added and .themixture .is stirred $011.30 minutes at.160 C. Yellow to copper. red colored -needles. are ,precipitated in good yield, sucked off after .cooling, washed .with .some formamide and .alcohol .and dried. .They.contain:35.83% of -C, 3.18% .o f.H,f7.67% .of.."Q,'.14.'89!%.of.lN,'.35.70% .of Cu. $44,.partsof' the .copper compoundthus obtained are ;.introi:luced.at,0 :C. with cooling and stirring..into-..3000 ;,parts1.o'f-.nitric iac'id lhaving .a. specific 4 gravity of 1-5 After stirring for half an hour the red crystals are dissolved. Copper nitrate precipitates and is separated by filtration. The filtrate is then stirred into ice and the precipitated nitrate of amino-imino-isoindolenine is sucked oil, washed neutral with cold water and dried.

Amino-imino-isoindolenine may also be obtained in equally good yield on carrying out the reaction under the same conditions, however, replacing the above-said complex copper compounds by those obtained as described in the following:

(a) A mixture of 147 parts of phthalimide, 180 parts of urea, 0.3 part of ammonium molybdate, 500 parts of nitrobenzene is stirred for one and a half hours at 160 to 170 C. Into this mixture are introduced 110 parts of cuprous chloride and kept for one and a half hours at 170-180" C. First a yellow crystalline precipitate is formed which soon becomes red brown. 450 parts of formamide are added and stirred for a further 90 minutes at 160 C. The crystalline precipitate having changed to orange red and obtained in good yield is sucked off while hot, washed with hot nitrobenzene and formamide, then washed with cold ethanol and dried.

(b) 148 parts of phthalic anhydride are heated with 1200 parts of urea, 200 parts of cuprous chloride and 1 part of ammonium molybdate to 190-200 C. until the initially thinly liquid melt has been converted to a viscous paste. The reaction mixture is then diluted by adding 600 parts of nitrobenzene and further stirred for about one hour at 190-200 C. Further processing and isolation are achieved by diluting the mixture with 1130 parts of formamide, stirring for some time at 140-150" C., sucking off after further cooling and diluting with 800 parts of ethyl alcohol, washing the filtrate with hot formamide, hot water and alcohol and drying.

The reaction product obtained in excellent yield and purity has the following composition:

Per cent C 30.3 H 2.7 O 12.1 N 21.6 C1 2.9 Cu 28.1

Example 62 A mixture of 130 parts of phthalonitrile and 150 parts of cuprous chloride is introduced at 150 C. in portions into 1700 parts of formamide with stirring within about 60 minutes.

The temperature is then raised to 180-200 C. and a smooth current of air conducted over the vigorously agitated reaction mixture. Thereby the initially yellow orange to light brown colored precipitate changes to a bronze colored to deep dark red rhombic crystallizate which is sucked off at 7080 C., washed successively with formamide, water and methanol and dried.

The intermediate product thus obtained has the following composition: 33.8% of C, 2.2% of H, 0.4% of O, 14.5% of N, 7.1% of Cl, 41.1% of Cu.

305 parts of this compound are introduced in portions with vigorously stirring within 30 minutes into 1460 parts of an 80% nitric acid pro-cooled to C. and kept at this temperature. The reaction mixture is stirred until a uniform greenish-white coloration is obtained, which happens after about 30 minutes.

The mixture is subsequently sucked off from the copper nitrate and the filtrate is washed again with about 290 parts of concentrated nitric acid. The combined filtrates or the non-filtered reaction mixture containing copper nitrate are introduced with stirring into an appropriate quantity of ice. The precipitation occurring is complete after about 30 minutes. The precipitate is sucked ofl, washed neutral with cold water and dried. The amino-imino-isoindolenine nitrate thus obtained is practically pure. The yield amounts to 184 parts corresponding to 85.5% of theory calculated on the phthalonitrile used as starting material.

Example 63 400 parts of copper acetate are dissolved at 100-120 C. with stirring in 4500 parts of formamide. 204 parts of 3.4-dicyano diphenyl are introduced into this mixture which is stirred for half an hour at 160 C. Orange colored needles precipitate in good yield and are sucked off after cooling and washed with some formamide and alcohol and dried. According to analysis the substance contains the elements C, H, O, N, Cu in the ratio 14:l1:0.4:3:l.8.

420 parts of the orange colored compound are introduced at 0 C. with stirring into a mixture of 1500 parts of nitric acid (specific gravity 1.5) and 1000 parts of water. After half an hour the mixture is stirred into ice, the weakly yellowish, crystalline precipitate of 1-amino-3-imino-5 (or 6)-phenylisoindolenine-nitrate is sucked off, washed neutral with water and dried. By treatment with the equimolecular quantity of caustic soda solution the free base is obtained from the nitrate as hydrate. Nitrate and base dissolve in concentrated sulfuric acid with yellow coloration.

Example 64 2 parts of the intermediate product containing copper obtained according to Example 61 or 62 are suspended in 20 parts of cold glacial acetic acid. Within about 30 minutes 3 parts of cold nitric acid are added while vigorously stirring and decreasing the temperature to 0 C. Stirring is continued until the reaction mixture contains no longer any colored intermediate product. The white to greenish grey colored reaction mixture is introduced into ice and water until no more amino-imino-isoindolenine nitrate is precipitated by further dilution and the product is obtained in excellent yield and purity by sucking off, washing until neutral and drying.

Example 65 1 part of the intermediate product containing copper prepared according to Example 61 or 62 is introduced with stirring at 0-l0 C. into 10 parts of 20% fuming sulphuric acid and agitated at that temperature until the reaction mixture has become colorless. Then the solution is brought into a mixture consisting of ice, 2-3 parts of potassium nitrate and about 16 parts of sodium bicarbonate.

At the end of this working stage the reaction is to be neutral or weakly acid. The amino-imino-isoindolenine nitrate precipitating in a crystalline form is very purely obtained by sucking off and washing with a large amount of water. It can further be purified by boiling oil with methanol.

Instead of the mixture of potassium nitrate and sodium bicarbonate also other compositions may be used, such as ammonium nitrate, ammonia, or the sodium salt of naphthalene-l-sulfonic acid and ammonia. In the latter case the amino-imino-isoindolenine precipitates as the salt of naphthalene-l-sulfonic acid which is diflicultly soluble in water.

Example 66 60 parts of copper acetate are dissolved in 254 parts of formamide with stirring at -120" C. and 25.4 parts of 3.3.4.4'-tetracyanodiphenyl are introduced into the solution. After half an hours stirring at C. orange colored needles precipitate which after cooling are sucked off, washed with some formamide and alcohol and dried. The yield amounts to 51 parts.

51 parts of the complex copper compound thus obtained are introduced at 0 C. with cooling and stirring into 500 parts of nitric acid of the specific gravity 1.5. After half an hours stirring the orange colored crystals have gone into solution and copper nitrate has deposited. After stirring into ice colorless needles of the nitrate of 6.6' di- .29 (amino-imir1o-isoindoleninyl) precipitate --vyhi qh .a zler tsucking oil are washed neutral with water 2 andv .dried.

,Ondecomposing the copper complex compounds -.with ,asolution of 51 parts of potassium cyanide.in 250 parts bytvolumecof water at -10 Cplnstead of .using ?nitric .acid, 6.6-di amino-3-imino-isoindoleninyl) is.- obtained, as freeibase.

Example 67 Example 68 p 11 parts ofphthalonitrile and 13 parts .of :cuprous chloride are heated in 100 parts of quinolineat 1'2'0-1'40" =C. for ten hours while passing over dryammoniargas. lhereupon the'mixture is cooled down toroomztemperature under gaseous ammonia, washed with alcohol "and dried. 22 parts of a technicallypure complex compound .Qfthfi probable composition (CaH7NaCu)2CuCl are.thus .pbtained. :By aftertreating with aqueous ammonium .chlori'de-ammonia solution, methanol and acetone the .brick redcomplexsalt may be obtained in analytically pure form. By treatment with nitric acid while using the. same pr o- ;portions.of.ingredients and following the procedure as described in Examples 61 and 62 the nitrate of arnin ogiminoeisoindolenine is obtained in goodyield.

Example 69 -wasliing-w ith cold water.

Example 70 128 parts of phthalonitrile are stirred with 150 parts of c uprouschloride and 1000 parts of ethanol in a closed ,30 2 amm ni A" ,re br wn learne it m e tw i i s aminorimino isoindolenine.remains-behind. .The; reaction product does not contain any phthalonitrile. ,Aminoimino-isoindolenine maybe obtained as nitrate from the 7 reaction product by meansofconcentrated nitric acid as vessel and ammonia gas is introduced untilthe phthalonitrile hasdisappeared from the reaction mixture. "The 'reactionis--accomplished at room temperature at normal pressure.

A 'briclered, microcrystalline copper compound -cont ai ning amino-imino-isoindolenine is formed from which -+'-as indicated in Example 6l--the nitrate of aminoimino-isoindolenine may be obtained by meansofcon- "centrated'nitric acid. In case atrnosphericoxygen'has not.been excluded during reaction the brick-redcrystal powlder contains some blue grey crystals.

The .product'treated with boiling formamide exhibits the following composition:

immat rial] Exampleifil.

"Exnmple72 ,22 parts ,of .1:anilino-3riminorisoindolenine melting 0 ,point .207 C.;) --ar;e-intrQdUQBd.into..69 parts .of :boiling tetraline. The solution is rapidly orange colored with the evolution of ammonia. Boiling is stopped after 3-4 miniltQS,iIhBQSQllltlQntlSnGQQlQdgtO ahOUt 100 Cuflfld sucked otf. The res duecconsistsaofraysmallequantity (about-0.8 5 ma t)rofi e y ry alfized, me alafre phthalocyanine- -Qn1d iluting=the brownzorangezcolored .filtrate with One randarhalf. times the guantity oflmethanolweakly orange ycolored needles precipitate. .Aft er coolingithe precipitate is suekedsofi washedvwith rnethanohand dried. ,-The 0 yield amounts-;t o6:.5,parts. iQmboilingforadonger time the yield of the orange red product is reduced. The product is readily solublednhotbenzene and crystallizes :byiaddingmethanol in:;felted,:brownish red needles melt- .=ing at318t7 C. According'to'ianalysis:QC=79.15, H=A-.6, 5. SN-=I 31-5 %1) the reaction profductis:arcondensatiomprod- 1110i; consisting :of :42 r-mols -of :1-anilino-i3+imino;-isoindolent'neihavingasplitzolfronermol of NH3 .0r .0f "53 mols of taminoephenybiminophtbalimifde thawing split -ofi :2 mols of NH3. 0 The orange red colored product melting at 187 C.

is slightly soluble in methanblfhowever, immediately dissolves withrdeeprorange yellow coloration byadding sodium hydroxideisolution. EBysadding somenwaterandihyrdrosulfite to the mixture-aninitiailyigreengthereafter-blue, 5 evat' -li'ke solution is::obtained:which'= is decolorized onheatain'g. i I

l &Example:76

24 parts or 1-oxethyl-amino 3-oxethyl imino-isoindolenine (prepared accor'ding'to' Example 59) are stirred with 100 ,parts ,of .acetic .,anhydri de, the temperature being ,allowedio raise 10.50 C. After one-hour the .excess ,anlrydride is decomposed by adding .ice, common .salt lsolu'tion is a'dded-to -the clear, solution in equal volume and the precipitated .1eacetoxethylfaminoriiaacetoxethybimino- ,I isoindolenine hydrochloride is isolated by conventional methods. The reaction prdductiis obtainedas colorless, readily soluble salt.

'Example :74

0 13'-parts of amino-imino isoindolenine and 30 parts of anesthesimare dissolved in 200*parts of anhydrous ethanol and the temperatureds*raised to 130 ;C.'while distilling thekslilcohcil. "The reaction is complete'd'within a short time. After stirring with cold alcoholysuckingotf and 5 dry-ing :19 parts of 'analytically pure, light-yellow l-(pcarbe'thoxy-phenyl)-amino=3aimino-isoindolenine melting at l98 200 (3. are obtained.

.ExamblefZS 0 The followingisubstances are' succes'sively .reacted in 100 parts of anhydrous ethanol at the said temperatures: 0.5 part of sodium atZO-SO C., 26 parts of phthaloniqtrile -at C., 40'parts of snlfanilic acid amide at Percent Q" =3 5 -45 'The mixturensjgradually cooled-"with stirring and the .255 crystallized '1 p-suIfOnyIamidO-phenyl) amino-S-imino-isob 0 9 indolenineis isolated in known manner. 50-51 parts N 15,17 "of a'ilight yellow productmelting af 2l-2" C. are obtained. Q- .Example 76 :c1

Example 71 autoclave with stirring and the temperature isvkeptwat 150 C. for 10 minutes. After cooling andnblowingrotf "-parts of phthalonitrile and 9 7 ';parts of. 3-chloro aniline are *reacted in *a. methylate'solution consisting of 2 parts of sodium and 5 0 parts of methanol at temperatures between 30 and 45 Al-rady after 30 minutes the 5 reat-ztion product begins gtogcrystallizezfrom the..clear.-solu- ..;tion.' :AfitenlQ-QO hoursqisplationgis accomplished in the 31 115-120 parts of pure, light-yellow 1-(3- melting at usual manner. chlorophenyl)-amino-3-imino-isoindolenine 214 C. are obtained.

Example 77 2 parts of sodium are dissolved in 150 parts of anhydrous methanol and in this solution 80 parts of phthalonitrile and 100 parts of 4-chloro aniline are caused to react. 105-110 parts of light-yellow 1-(4'-chlorophenyl)-amino- 3-imino-isoindolenine melting at 206 C. are obtained.

Example 78 78 parts of l-(3'-chlorophenyl)-amino-3-imino-isoindolenine (prepared according to Example 76) and 38 parts of 3-chloro aniline are heated in 100 parts of xylene at 150 C. for 7 hours, filtered at 100 C. and stirred when cold; the yellow crystallizate is sucked off when icecold, washed with benzine and dried. 91 parts of 1-(3' chlorophenyl) amino 3 (3" chlorophenyl) iminoisoindolenine melting at 150 C. are obtained.

Example 79 78 parts of l-(4-chlorophenyl)-amino-3-imino-isoindolenine (prepared according to Example 77), 39 parts of 4-chloro aniline and 100 parts of xylene are heated under reflux to the boil for 5-7 hours, all reactants being dissolved thereby. 96 parts of 1-(4'-chlorophenyl)- amino-3-(4"-chlorophenyl) -imino-isoindolenine melting at 150 C. are obtained.

Example 80 2 parts of sodium, 80 parts of 4-anisidine, 80 parts of phthalonitrile are successively dissolved in 100 parts of anhydrous methanol, the temperature being allowed to raise up to 40-50 C. After 24 hours the crystallized product is sucked off when ice-cold, washed and dried. 128 parts of 1-(4'-methoxy-phenyl)-amino-3-imino-isoindolenine melting at 190-195 C. are obtained.

Example 81 81 parts of 1-(4'-methoyphenyl)-amino-3-irnino-isoindolenine (prepared according to Example 80), 41 parts of 4-anisidine in 100 parts of xylene are heated to the boil for 6-8 hours and then cooled with stirring. 85-90 parts of 1-(4-methoxyphenyl)-amino-3-(4-methoxyphenyl)-imino-isoindolenine are obtained. The yellow product melts at 150-155" C.

Example 82 3 parts by weight of sodium are dissolved in 1000 parts by volume of methanol while stirring at room temperature. 160 parts of 2.3-dicyanopyrazine are introduced and a weak stream of gaseous ammonia is passed through the solution at 2030 C. The solution becomes reddish at the beginning, later on yellow and, after some hours, a grey crystalline precipitate consisting of 4.7- diaza-1amiuo-3-imino-isoindolenine forms to an increasing extent. After about 24 hours, the reaction product is filtered off, washed with methanol and acetone and dried. The yield amounts to 160 parts by weight.

Example 83 19.2 parts of 4-ethoxy phthalic anhydride (M. P. 119-120) are introduced at 80 C. with stirring into a homogeneous melt of 32.4 parts of urea and 19.2 parts of ammonium nitrate with the addition of 0.03 part of ammonium molybdate. By heating the melt foams between and C., a brown-yellow, almost clear melt forms at 174-176 C. After about 2 hours stirring a light crystalline precipitate forms almost instantaneously and the mixture becomes viscous. The mixture is diluted by quickly running in 100 parts of ice-cold Water, stirred until a homogeneous paste has formed, filtered oif, washed with water and dried. 22.6 parts of almost colorless nitrate of l-amino-3-imino-5-(or 6-)-ethoxyisoindolenine, which corresponds to 89 per cent of theory are obtained. The product decomposes at about 247 C. It yields the free base with aqueous caustic soda solution. The base decomposes at about 175 C. with the formation of a green melt.

In analogous manner the nitrate of l-amino-3-imino- S-(or 6-)methoxy-isoindolenine is obtained from 4- methoxy-phthalimide (M. P. of the pure product 216 C. uncorrected) or 4-methoxy-phthalic anhydride (M. P. 98-99 C.). The reaction product shows a decomposition point of 242-245 C. and dissolves in water somewhat more easily than the analogous product containing no methoxy group.

Example 85 8 parts of 4-methylmercapto phthalimide (M. P. 212- 213 C.) are introduced into a mixture of 12 parts of urea, 8 parts of ammonium nitrate, 9 parts of nitrobenzene, 0.1 part of ammonium molybdate at 130 C. and the mixture is gradually heated to 175 C. The solution which is clear at the beginning becomes yellowbrown on heating and fine, orange-yellow colored crystals precipitate after heating for about 3 hours. The reaction mass becomes soon very viscous; therefore, it is expedient to dilute the mixture with 20 parts of nitrobenzene. After a reaction time of 3 hours the mixture is diluted with methanol after cooling to 80 C. and suction filtered in the hot state. The reaction product is washed with methanol and water and thereafter dried. The nitrate obtained in good yield crystallizes in long lemon-yellow needles which melt at 236 C.

By reacting the nitrate with the calculated amount of caustic soda solution in a suspension of methanol and water l-amino-3-imino-5- (or 6-)methylmercapto-isoindolenine melting at 207-208 C. is obtained. The crystallized, weakly yellowish base dissolves in dilute acetic acid with an intensive orange-yellow coloration.

Example 86 A moderate stream of ammonia is passed over a suspension of 53.5 parts of phthalonitrile in 64 parts of a solution of ammonia in methanol containing about 12.5 parts of ammonia and 0.65 part of 19.25 per cent of a solution of caustic soda in methanol. The suspension is gradually heated to 60 C. and stirred at this temperature for about 1 /2 hours. The phthalonitrile dissolves after about 1%. hours, and l-amino-3-imino-isoindolenine (or its methanol addition compound) precipitates in coarse heavy crystals.

A small sample of the reaction mixture in a mixture of pyridine and water gives a blue leuco compound with dilute caustic soda solution and sodium hyposulfite.

After about 1 /2 hours this leuco compound of a sample has disappeared almost completely; 0.20 part of glacial acetic acid is then added and stirring is continued at 60 C. for about /2 hour While passing over ammonia until no blue leuco compound is any longer visible.

When carrying out the reaction on a large scale production it is not necessary to precipitate the 1-amino-3- imino-isoindolenine in pure form. In this case it is sufficient to evaporate the reaction mixture to dryness in vacuo. About 62.1 parts of an almost colorless to faintly greenish product containing about 90.6 per cent of pure product, which corresponds to a yield of about 93 per cent of theory, are thus obtained.

Example 87 20.4 parts of 3.4-dicyano-diphenyl and 24.4 parts of a 10.5 per cent of solution of ammonia in methanol are introduced into the solution of 0.45 part of caustic soda in 48 parts of methanol and the mixture is stirred at 40-50 C. The dinitrile dissolves during 4-6 hours.

The solution is neutralized with 0.68 part of glacial acetic acid and concentrated to a small volume. The resulting 1-amino-3-imino-5-(or 6-)phenyl-isoindolenine can be isolated by stirring the concentrated methanol solution with about 80 parts of toluene and subsequently evaporating the solvent in vacuo. The product is obtained as loose powder in a yield of over 90 per cent.

Example 88 250 parts of ground phthalonitrile are mixed while stirring with 500 parts by volume of liquid ammonia in an autoclave at 140 C. under a pressure of 105-110 atm. for -7 hours. After cooling the ammonia is blown off and the light-grey, partially coarsely crystalline residue is mechanically removed and the mixture is heated to 95 C. About 285 parts (corresponding to about 98 per cent of theory) of almost pure 1-amino-3-imino-isoindolenines are obtained. It is soluble in three times its quantity of water at 60 C. and crystallizes from its concentrated aqueous solution in long, colorless needles in form of a hydrate which can be dried at low temperature. The hydrate thus obtained can further be dried at 90-95" C. without the danger of saponification, the anhydrobase being thus obtained. The pure anhydrobase melts at about 194-196 C. with green coloration and evolution of ammonia. By prolonged heating the aqueous solution having a strongly bitter taste the product is saponified to form mono-imino-phthalimide and, finally, phthalimide with the evolution of ammonia.

Upon addition of nitrate-, phosphate-, sulfiteor perchlorateions the corresponding colorless, very difiicultly soluble salts precipitate in crystals in an almost quantitative yield.

The anhydrobase and its hydrate easily dissolve in methanol already in the cold but are very slightly soluble in ether, acetone, benzene and cyclohexane, even in the heat. The base quickly dissolves in higher boiling solvents such as nitrobenzene and dichloro benzene and even in pyridine with green coloration and evolution of ammonia and partial formation of metal free phthalocyanine. By mixing the l-amino-3-imino-isoindolenine with glycol while stirring a crystallized addition product, which is more fully described in Example 28, is obtained. By heating the addition product with metallic salts, par ticularly in the presence of solvents, under suitable, weakly reducing conditions the corresponding metal phthalocyanines are obtained With the splitting oil of ammonia, mostly in a very good yield and even at water bath temperatures.

By shaking the aqueous solution of the base with benzoyl chloride in the presence of alkali a dibenzoyl compound forms, which is obtained from benzene in form of light yellow, bright, coarse crystals in a pure form at l76-177 C.

calculated for found 22Hl5 2 3 C=74. 95% C=74 77% 4. 20% H= 4. 28% N=1L 65% N=11. 89%

Example 89 increases.

34 By introducing 500 parts of water with stirring, the reaction product precipitates in light yellow crystals. The yield amounts to per cent of theory. The base, C1sH25N5=l-(l-piperidyl-amino)-3-(l-piperidyl-imino)-isoindolenine is obtained analytically pure from pure starting materials. The base can be purified by recrystallizing from gasoline or another organic solvent, or by dissolving in an alcohol and precipitating with water. The base dissolves in dilute acids but not in pure water.

Example 40 parts of technical 2-amino-naphthalene-S-sulfonic acid and 10 parts of 1-amino-3-imino-isoindolenine are dissolved in 160 parts of methanol. 50 parts of glacial acetic acid and the dark orange colored crystalline precipitare is suction filtered. The reaction product (34 parts) is apparently an internal salt of 1-(2-naphthyl-5-sulfonic acid)-arnino-3-imino-isoindolenine. It is only very sparingly soluble in water and organic solvents. No medium suitable for recrystallization has been found so far.

Example 91 In 25 parts of methanol are dissolved 4 parts of lamino-3-imino-isoindolenine and 9 parts of a paraflin amine of the statistical molecular weight 194 which is obtained from the socalled first runnings of fatty acids via the ketones obtainable therefrom according to conventional methods. By stirring the solution at 20 C. for two hours, the amino group of the isoindolenine derivative is exchanged for the parafiin amine. The reaction product which crystallizes is filtered oil at 0 C., washed with some cold methanol and dried. 3.2 parts of paraffinarnino-imino-isoindolenine is obtained which, according to analysis, has the statistical summation formula C2a.7H32.2N3.

The base can be recrystallized from light gasoline.

Example 92 20 parts of l-paraffin-amino-3-imino-isoindolenine, 20 parts of ethanolamine, and 20 parts of glacial acetic acid are successively dissolved in 160 parts of methanol and the solution is stirred at room temperature. After 30 minutes 1-hydroxyethyl-amino-3-hydroxyethyl-imino-isoindolenine begins to crystallize. Stirring is continued for another hour and the reaction product Which is obtained in a quantitative yield is isolated by filtering, washing with water and drying.

Example 93 20 parts of 1-anilino-3-anilo-isoindolenine-hydrochloride are suspended in parts of methanol and 10 parts of ethanolamine are added. The solution which is dark yellow at the beginning gradually becomes lighter and 1 hydroxyethyl amino 3 hydroxyethyl imino isoindolenine soon begins to crystallize in almost quantitative yield. The product is isolated as described in the preceding example.

Example 94 18 parts of hexamethylene diamine and 20 parts of phthalonitrile are reacted in the sodium methylate solution prepared from 0.5 part of sodium and 80 parts of methanol at 40-50 C. An amino-imino-isoindolenine derivative (CsHeNs(CH2)eNH2 Which is substituted with one aminohexamethylene radical is formed. The reaction mixture is diluted with another parts of methanol as soon as the reaction, which is exothermic at the start, is complete.

The solution is further stirred at room temperature for a prolonged period, at least 24 hours. The product slowly crystallizes in a yield of 34 parts which, according to analysis, represents N .N -cyclohexamethylene-1- amino-3-imino-isoindolenine formed by intramolecular amine exchange reaction to which two molecules of methanol are attached.

EN +2CH;OH F mo-218 C.

The product can be recrystallized from methanol (dissolution and crystallization proceeds very slowly); by boiling with acetic acid anhydride and pyridine the product yields the acetyl derivative CsI-I4Ns(CHz)sOCOCH2 (M. P. 154 C.) which is liberated from methanol.

Example 95 15 parts of 1-amino-3-imino-isoindolenine, and 40 parts of 4-amino-azo-benzene are heated in 200 parts of xylene until no ammonia is any longer split oil. When cooling the dark orange colored 1-benzene-azo-anilino-3benzeneazo-anilo-isoindolenine crystallizes in good yield. The product is isolated by filtering and washing with cold methanol.

Example 96 24 parts of 3.4-dicyano-diphenyl are reacted with 20 parts of 4-amino-diphenyl in a solution of 0.5 part of sodium in 160 parts of methanol.

1 (4 phenyl) anilino 3 imino (or 6-)- phenyl-isoindolenine obtained in a quantity of 27.5 parts is heated to the boil in 13 parts of 4-amino-diphenyl in 200 parts of xylene whereby 50 parts of xylene are slowly filtered off. When cooling and/or diluting with a mixture of petroleum and ether the dark-yellow colored 1' (4' phenyl) anilino 3 (4" phenyl) anilo 5-(or 6-)phenyl-isoindolenine crystallizes. The product is isolated by filtering and washing with petroleum and ether.

Example 98 20 parts of 1-amino-3-imino-4-(or 7-)aza-isoindolenine nitrate are dissolved in 50 parts of 2-amino-ethanol 8.8 parts of 1 thiomethyl 3 imino isoindolenine (weakly cream-colored needles which melt at 102-103 C. with evolution of gas and formation of a blue melt) are boiled with reflux with 8 parts of ammonium nitrate in 80 parts of methanol. Already after some minutes a greenish-grey, slightly soluble product precipitates and methyl mercaptane escapes. The product (about 5 parts) which is isolated after one hours heating under reflux, cooled to 40 C., suction filtered and washed with methanol, substantially represents the nitrate of l-amino- 3-1mino-isoindolenine. By dissolving the product in cold dilute caustic soda solution, filtering off the non-dissolved, colored contaminations and precipitating the clear, almost colorless filtrate with glacial acetic acid with the addition of some ammonium nitrate, the nitrate of l-amino- 3-imino-isoindolenine is obtained in colorless, sandycrystalline form (M. P.=293-294 C.). By replacing ammonia by aniline or ethanolamine the correspondingly substituted 1-amino-3-imino-isoindolenine derivatives are obtained in good yields.

1-thiomethyl-3-imino-isoindolenine is obtained by finely grinding 16.2 parts of imino-thio-phthalimide (prepared according to Example 52) with 320 parts of Water, heating the suspension formed to 60 C. and mixing with 25 parts by volume of caustic soda solution (40 per cent). The solution thus obtained is quickly filtered and quickly cooled to 20 C. by addition of ice. By stirring the resulting clear, brown-yellow solution with 15 parts of dimethyl sulfate at room temperature Weakly yellowish colored crystals precipitate after a short time. The precipitate is filtered otf, washed with cold water and dried in the exsiccator. The yield amounts to 12 parts. The crude l-thio-methyl-3-imino-isoindolenine is unstable on exposure to higher temperatures and light. It melts at about C. with evolution of gas and formation of a dark green-blue colored melt. By dissolving the melt in methanol at a max. temperature of 40 C. and slowly diluting with water the product is obtained in creamcolored needles of the melting point 102-103 C. after green coloration from 85 C. By heating the thiomethyl ether in nitrobenzene and even in glacial acetic acid metalfree phthalocyanine is obtained.

Example A weak current of ammonia is passed over a suspension of 0.28 part of methanolic caustic soda solution (19.25%) 19.8 parts of methanolic ammonia (corresponding to 3.75 parts of ammonia) and 7.19 parts of 4-ethoxyphthalonitrile (prepared by splitting off water from 4- ethoxy-phthalamide, M. P. 133l34 C.) until the 4- ethoxy-phthalonitrile has dissolved and 4-ethoxy-phthalonitrile is no longer precipitated from a sample of the suspension on diluting with water and some drops of caustic soda solution. Thereupon 0.08 part of glacial acetic acid is added and ammonia is passed over the solution for another /2 hour. By evaporating the solution 5-(or 6-)ethoxy-l-amino-3-imino-isoindolenine is obtained as light crystalline powder which contains only small quantities of sodium acetate and can be employed immediately for further reaction. The crude product becomes greenish at 166-174 C. and decomposes at l76l77 C. with foaming. It is easily soluble in methanol and dilute acetic acid and difiicultly in acetone. The yellow solution in hydrochloric acid is quickly decolorized by hydrolysis of 5-(or 6-)ethoxy-1-amino-3- imino-isoindolenine. The slightly soluble nitrate of the base can be precipitated by mixing the methanolic aqueous solution with ammonium nitrate solution and weakly acidifying with acetic acid. The nitrate which can advantageously be utilized for producing the pure base is weakly lemon-yellow colored. It becomes darker at 240 C. and decomposes at 244245 C. with foaming.

By decomposing the nitrate suspended in methyl alcohol with the calculated amount of caustic soda solution and diluting the resulting solution with water, the pure base is obtained in small, coarse crystals which decompose at 179-180 C. By replacing ammonia by primary or secondary amines the correspondingly substituted isoindolenine derivatives are obtained.

Example 101 When replacing in the preceding example 4-ethoxyphthalonitrile by the equivalent amount of 4-phenoxyphthalonitrile (prepared by splitting oft water from 4- phenoxy phthalamide, M. P. 101l02 C.) a solution of 5-(or 6-)phenoxy-l-amino-3-imino-isoindolenine is obtained. By evaporating the solution the base remains behind as a brittle, yellow colored mass which can easily be pulverized. The mass is easily soluble in methanol, difficultly soluble in acetone and shows properties similar to the ethoxy compound described in the preceding example. The slightly soluble nitrate of the base, which is strongly lemon-yellow colored, becomes dark at temperatures above 250 C. and decomposes at 264-265 C. with foaming. The base prepared from the nitrate melts at 94-96 C. to form a dark green liquid which decomposes at 10ll02 C. with foaming.

The syntheses described in the foregoing paragraphs B, C and D are equivalent to each other, i. e. it is possible to produce any l-amino-3-imino-isoind0lenine derivative directly from dinitrile by addition of an amine as well as by exchange of the alkoxy or amino group in the corresponding l-alkoxyor 1-amino-3-imino-isoindolenine derivatives for the same amine. In the foregoing examples the processes according to paragraphs B, C and D are interchangeable as will be apparent to anyone skilled in the art. Therefore it is unnecessary to specifically describe each of these processes for each and every isoindolenine derivative hereinbefore described, the disclosure of one process constituting also a full disclosure of the other possible methods. Furthermore each 1- amino-B-imino-isoindolenine derivative obtainable by the method of production according to paragraphs A and B may also be obtained by the processes described in paragraphs B, C and D.

We claim:

1. The process for the production of 1-amino-3-iminoisoindolenines which comprises dissolving out the monovalent copper from the yellow to red-colored copper complex compounds obtainable by heating up to temperatures of about 200 C. an o-arylene derivative having no more than two rings and selected from the group consisting of o-arylene dicarboxylic acids, the anhydrides, N-unsubstituted amides and N-unsubstituted imides thereof; a compound selected from the group consisting of urea and biuret; ammonium molybdate and a soluble copper salt, by treating said complex compounds at temperatures up to about 30 C. with an agent selected from the group consisting of nitric acid, concentrated sulfuric acid and an aqueous solution of an alkali metal cyanide.

2. The process as claimed in claim 1 wherein the copper dissolving agent is nitric acid.

3. The process as claimed in claim 1 wherein the copper dissolving agent is concentrated sulfuric acid.

4. The process as claimed in claim 1 wherein the copper dissolving agent is an aqueous solution of an alkali metal cyanide.

5. The process as claimed in claim 1 wherein the copper dissolving agent is concentrated sulfuric acid containing sulfur trioxide.

6. The process as claimed in claim 1 wherein the copper dissolving agent is concentrated sulfuric acid containing hydrogen peroxide.

No references cited. 

1. THE PROCESS FOR THE PRODUCTION OF 1-AMINO-3-IMINOISOINDOLENINES WHICH COMPRISES DISSOLVING OUT THE MONOVALENT COPPER FROM THE YELLOW TO RED-COLORED COPPER COMPLEX COMPOUNDS OBTAINABLE BY HEATING UP TO TEMPERATURE OF ABOUT 200*C. AN O-ARYLENE DERIVATIVE HAVING NO MORE THAN TWO RINGS AND SELECTED FROM THE GROUP CONSISTING OF O-ARYLENE DICARBOXYLIC ACIDS, THE ANHYDRIDES, N-UNSUBSTITUTED AMIDES AND N-UNSUBSTITUTED IMIDES THEREOF; A COMPOUND SELECTED FROM THE GROUP CONSISTING OF UREA AND BIURET; AMMONIUM MOLYBDATE AND A SOLUBLE COPPER SALT, BY TREATING SAID COMPLEX COMPOUNDS AT TEMPERATURES UP TO ABOUT 30* C. WITH AN AGENT SELECTED FROM THE GROUP CONSISTING OF NITRIC ACID, CONCENTRATED SULFRIC ACID AND AN AQUEOUS SOLUTION OF AN ALKALI METAL CYANIDE. 